Physics and Chemistry

of the
Interstellar Medium
Sun Kwok
The University of Hong Kong

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UNIVERSITY SCIENCE BOOKS
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Kwok, 5. (Sun)
Physics and chemisu'y of the interstellar medium I Sun Kwoit.
p. cm.
Includes bibliographical references and index.
lSBN 1-391389-46-7 (alk. paper)
1. Interstellar matter—Textbooks. 2. Astrophysics——Textbooks.
3. Cosmochemistry—Textboolts. 1. Title.
QBT90.K96 2006
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Printed in the United States of America

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Contents

Preface xi

The Interstellar Medium 1

1.] States of Matter in the [SM 2
1.2 Interactions between Stars and the ISM 3
1.3 Chemical Abundances in the ISM 5
L4 The Coupling between Interstellar Matter and Radiation 7
1.5 Emission Nebulae and the Ionized Component of the ISM 9
[.6 Reflection Nebulae 12
L7 Dark Clouds and Molecular Clouds 14
1.3 Diffuse Interstellar Clouds and Infrared Cinus 14
1.9 Hot Gas and Galactic Corona 17
HO Multiple Phases of the ISM I7
1.] 1 Summary 20

Fundamental Concepts of Radiation 21

2.1 Intensity 22
2.2 Flux 24
2.3 Moments of Intensity 29
2.4 Thermodynamic Equilibrium vs. Steady State 30
2.5 Blackbody Radiation 34
2.6 The Equation of Transfer 36
2.? Solutions to the Equation of Transfer 40
2.3 Numerical Soluuon to the Equation of Transfer 44
2.9 Scattering 46
2. l0 Polarization 49
2.1 1 Summary 49
vi Contents

3 Measurements of Radrhtion 53
3.1 Flux Measurements 54
3.2 Measurement of Intensity 6]
3.3 Spectroscopy 73
3.4 Summary 74

4 Photoionization and Recombination 77

4.1 The Hydrogen Atom 78
4.2 Spectroscopic Notation 30
4.3 Bound-Free Transition 35
4.4 Bound—Free Absorption in a Stellar Atmosphere 87
4.5 Recombination B9
4.6 Ionization Structure of a Static Nebula 92
4.? Diffuse Interstellar Radiation Field 94
4.8 Ionization of Complex Atoms 96
4.9 A Dielectronic Recombination 97
4.10 Charge—Exchange Reactions 99
4.11 Summary 99

5 Line Radiation from Atoms and Ions 103

5.1 Permitted and Forbidden Transitions 104
5.2 Transitions within Multiplels 1 13
5.3 Fine-Structure Lines 115
5.4 Hyperfine Lines 122
5.5 Absorption and Emission 125
5.6 Spectral Line Formation 127
5.7 Scattering Cross Sections 132
5.3 Line Broadening 136
5.9 The Voigt Profile 139
5.10 Equivalent Width and the Curve of Growth 141
5.11 Recombination Lines 142
5.12 Collisionally Excited Lines 151
5.13 Resonance Fluorescence 160
5.14 Recombination Lines of Metals 161
5.15 Statistical Equilibrium and Population Distribution 163
5.16 Determination of Nebular Density and Temperature by Diagnostic
Diagrams 163
5.17 Atomic Parameters 164
 Contents vii

5.13 Abundance Determination by Absorption Spectroscopy 165

5.19 Abundance Determination in Emission Nebulae 166
5.20 Summary 167

Continuum Radthtt'on in the Gas Phase 17]

6.1 Free-Bound Continuum Radiation 171
6.2 Two-Photon Radiation 172
6.3 Free—Free Continuum Emission 176
6.4 Electron Scattering 131
6.5 Heating and Cooling of Phatoionized Regions 132
6.6 Determination of the Temperature of the Central Star by Nebular
Properties 185
6.7 Summary 186

Interstellar Molecules 189

7.1 Molecular Transitions I92
7.2 Electronic Structures of Molecules 192
7.3 Molecular Orbitals and Hybridization 195
7.4 Rotational Transitions 196
7.5 Vibrational Transitions of Dietomic Molecules 200
7.6 Electronic Transitions 204
7.7 Effects of Nuclear Spins on Rotational Spectra 206
7.3 Rotational Spectra of Symmetric Tops 213
7.9 Asymmeu'ic Rotators 224
7.10 Radicals 236
7.1 1 Molecular Ions 247
7.12 Molecules Containing Metals 249
7.13 Raman Scattering 252
7.14 Summary 254

Vibrational Spectroscopy of Polyatomic Molecules 257

3.] Linear Molecules 253
8.2 Symmetric Tops 264
3.3 Asymmetric Tops 263
3.4 Carbon Chains 270
3.5 Polycyclic Aromatic Hydrocarbons 275
3.6 Summary 277
vlll Contents

9 Molecular Excitation and Abundance Determination 279

9.1 Partition FuncliOns and Thermal Distribution 279
9.2 Deriving the Rotational Excitation Temperature 231
9.3 Excitation of Molecules 281
9.4 Deriving Molecular Abundance from Linc Observations 235
9.5 A 'hvo-Level Molecule under Collisional Excitation 287
9.6 A Two—Level Molecule under Collisional and Radiative Excitation 289
9.7 Optically Thick Lines and Non-LTE Population Distribution 291
9.3 Molecular Abundance by Absorption Spectroscopy 293
9.9 OrtholPaIa Ratios 295
9.10 Isotopic Abundance 295
9.1 1 Isomers 296
9.12 Conformers 300
9.13 Summary 301

10 Interstellar Grains: Physical Processes 303

10.1 Interstellar Extinction 305
10.2 Dust Absorption and Scattering 308
10.3 Dust Emission 31 1
10.4 Thermal Coupling between the Dust and Gas 313
10.5 ReflectiOn and Scattering 319
10.6 Dust Absorption in the X-Ray Region 320
10.7 Stochastic Heating 321
10.3 Interstellar Polarization 322
10.9 Photoelectric Effect 323
10.10 Grain Processing 323

11 The Chemical Composition of Interstellar andr Circumstellar

Grains 327
1 1.1 Optical Properties of Solids 328
11.2 Inorganic Compounds 329
l 1.3 Organic Compounds 343
1 1.4 Summary 352

12 Carbonaceous Grains 353

12.1 The Aromatic Infrared Bands 357
12.2 The 2175-A Absorption Feature 366
 Contents ix

12.3 The Diffuse Interstellar Bands 367

12.4 Extended Red EmiSSion 363
12.5 The 21-,um Feature 371
12.6 The 30-pin Feature 372
12.7 Plateau Features 373
12.3 Photochemistry 375
12.9 Summary 376

The Origin ofInterstellar Dust 377

13.1 The Formation of Dust in the Atmospheres of AGE Stars 373
13.2 Models of Carbonaceous Dust 379
13.3 Laboratory Simulations of Cosmic Dust 381
13.4 UV Processing of Ices 335
13.5 Interstellar Dust and the Solar System 337
13.6 Possible Enrichment of the Solar System by Interstellar Grains 395
13.7 Summary 396

Chemicai1 Reactions in the ISM 397

14.1 An Example: CO Chemistry 397
14.2 Photodissociation 401
14.3 Attenuation of the Radiation Field 404
14.4 Cosmic Ray Ionization 407
14.5 Gas-Phase Reactions 407
14.6 A Rate Equation 413
14.7 Photon-Dominated Regions 414
14.3 Grain—Surface Chemistry 413
14.9 Summary 423

15 Gas Dynamics, Gravitational Collapse, and Stellar Winds 425

15.1 Hydrodynamical Equations 425
15.2 Self-Gravitating Hydrostatic Spheres 429
15.3 The Virial Theorem 435
15.4 Pressureless Gravitational Collapse 437
15.5 Gravitational Instability 433
15.6 Stellar Winds from Hot Stars 440
15.7 Winds from AGB Stars 443
15.3 Systematic Motions in Star Formation Regions 454
15.9 Summary 456
x Contents

16 Interaction between Stars and the Interstellar Medium 461

16.] Supersonic Dynamics 46]
16.2 Supernova Remnants 466
16.3 Interstellar Bubbles 470
I64 Interacting Stellar Winds 477
16.5 The Momentum Paradox 486
16.6 Summary 488

17 Beyond the Galaxy 49I

l7.l Overall Stnictute of the [SM 49]
17.2 Radiative lnteracLionS berween Different States of Matter 492
[7.3 Application to Extragalactic Astronomy 494

£_—PPENDIX
1 Vector Formulae in Difi’erent Coordinate Systems 509

A_F_—PENDIX
2 Ionization Potentials for Atoms and Molecules 51 I

3.
APPEND List ofInterstellar Molecules 5I 7

A____PPENDIX
; Solutions to Selected Exercises 52}

Symbols and Abbreviations 535

Glossary 54 I
References 545
Index 559
Preface

The history of astrophysics has been a Series of successful applications of modern

physics to cosmic phenomena. In the 20th century. we saw the success of the applica-
tion of nuclear physics to the understanding of the energy generation of the Sun and
the stars, the synthesis of elements, and the change in nuclear processes as the driving
force for stellar evolution. The application of atomic physics was instrumental in our
understanding of the spectra of stars and gaseous nebulae. The measurements of the
strengths of electronic transitions of elements allow us to determine the abundance
of elements and to test the models of nucleosynthesis.
The discipline ofastrochemistry began with the development of millimeter-wave
astronomy in the early 19705. leading to the detection of rotational transitions of
over 120 molecules. The advent of infrared spectroscopy. in particular from space
missiOns. has made possible the detection of complex organic molecules through their
stretching and bending vibrational modes. Astrochernistry is not only interesting as
part of the study of the interstellar medium, but also relevant to the question of the
origin of life. Astrobiology is a rapidly growing field. and its importance is reflected
in this book by the inclusion of organic chemistry relevant to astronomy.
The developments in space observations. in particular in the X-ray (ROSAT.
Chandra), ultraviolet (IUE. FUSE). optical (HST). infrared (IRAS. ISO. Spirzer).
and submillimeter (SWAS. Odin) regions. have revolutionarized our understanding of
the interstellar medium. These new techniques have greatly expanded the range of
physical processes that can be studied in the interstellar medium. Interstellar ions.
atoms. molecules. and solid materials can now be studied in the UV. optical. infrared.
and millimeter parts of the electromagnetic spectrum. These capabilities will be
further developed with the launch of Herschel and SOFM. Students will find the
fundamental materials in this book useful in the interpretation of data from these
missions.
Although this book is called the “Physics and Chemistry of the Interstellar Me-
dium" and is primarily written for researchers and students involved in ISM research.
many of the basic materials are applicable to problems in extragalactic astronomy. In
the past. extragalactic astronomers derived most of their information from photome-
try and spectroscopy ofa few emission lines. and it was thought thatjust some basic
understanding of stellar colors and recombination line theory would be sufficient.
After all, the spectra of normal galaxies are just the superposition of starlight and
active galaxies and quasars are too far away to exhibit many emission lines. How-
ever. as the power of telescopes increases. physical processes that previously were
observable only in our own galaxy will be observable in external galaxies. For ex-
ample. with infrared and submm observations. dust continuum emissions are now
 Preface

commonly observed in galaxies. The lessons that we have learned in how to interpret
spectra of dust clouds in the ISM are therefore extremely valuable. Widr modem large
optical telescopes. many atomic lines in the ultraviolet can now be detected in distant
galaxies as they are being redshifted into the visible region. The conditions under
which intercombination lines and collisionally excited lines arise are now relevant.
The construction of powerful mm arrays such as ALMA will make possible the detec-
tion of many molecular species in external galaxies. The greatly improved sensitivity
of Spitzer over ISO means that many of the infrared lines previously seen only in the
ISM are detectable in galaxies.

Goals and Philosophy

This book is based on class notes that I have developed over a period of 20 years
teaching a two-semester course in advanced astrophysics for senior undergraduate and
beginning graduate students at the University of Calgary. The intended readership is
a physics student who is familiar with basic physics topics such as electromagnetism.
atomic structures. and quantum mechanics. as well as a chemistry background at
the first-year university level. The increasing availability of computer codes to treat
various problems (e.g.. CLOUDY for photoioinimtion. Raymond-Smith for X-ray
spectra. DUSTCD for dust continuum transfer. etc.) has resulted in many students
treating these tools as black boxes without understanding the underlying principles.
The goal of the book is to prepare the readers with a fundamental background in
physical and chemical processes and to allow them to properly interpret modern
observations. In order to help achieve this goal. I have included many sample spectra
and images from actual observations to illustrate the theoretical concepts.
By sticking with fundamental principles and avoiding phenomenological descrip—
tions. 1 hope that the material in this book will stay relevant for a long time, and not
be made obsolete by changing models and fashions.
In undergraduate studies. students try to solve problems whose solutions they
know exist. In graduate studies. students are given a problem which has not been
solved before and try to solve it. As research scientists. we identify a problem.
formulate it in mathematical terms. and then solve them. When confronted with a
physical problem. we have to isolate the critical variables. the physical processes
involved. and the relevant equations to use. The key for a successful scientist is to
think physically. and not to be bogged down by mathematical details. In this book. I
try to emphasize these principles.
Instead of writing down the most general equations and seeking the most general
solutions—die common approach taken by many physics textbooks—l deliberately
limit all equations to the one-dimensional case to minimize mathematical complexity.
and to obtain panicular solutions for the simplest case. By this approach. I try to
highlight the physical meanings of each term. which may otherwise be obscured by
the mathematics. I hope this will prevent students from mechanically grinding through
equations without realizing their meaning.
Some readers may notice that many topics are related to research that I have
done overthe years. Since I am obviously limited and biased by my own background. I
 Acknowledgments rtiii

apologize to readers who think some topics are neglected or not covered as extensively
as they could be. For example. I have left out magnetic fields. turbulence, and high-
energy phenomena such as relativity and cosmic rays.

Acknowledgments

I started drafting this book from my own teaching notes about ten years ago. Since
administration. leaching and research activities take up most of my normal working
hours. the writing of this book. unfortunately. has to be relegated to hobby status.
Much of the material was written on airplanes. in airport lounges. hotel rooms, and
at home during evenings and weekends. Many sections were written during early
monting hours in foreign lands when l was up early suffering from the effects of
jetlag. The task of writing this book was made easier by modern computer software.
The manuscript was Written in MEX. the calculations performed using MATHCAD.
and many of the figures prepared using Adobe Illustrator and AXUM.
Over the course of writing this book, 1 have benefited from discussions and
inputs from many friends and colleagues. Various versions of the draft have been
in circulation in the astronomical community in the last five years and] would like to
thank everyoue who has commented on what they read. In panicular, I thank Kevin
Volk for many years of collaboration and for his ideas and contributions to various
sections of the book. The expert knowledge of Peter Bemath in atomic and molecular
physics has added greatly to the respective chapters. The pioneering work done by
Renaud Papoular. Walt Duley and Alan Tokunaga on organic compounds in space has
influenced my own drinking on this subject. I also benefited from the discussions with
Lou Allamandolla, Huan-Cheng Chang, Dale Cruikshank. Olivier Guillois, Thomas
Henning. Chun Ming Leung. Yvonne Pendleton. Scott Sandford. Far-id Salama, Diane
Wooden. Li-Hong Xu. and many others on different aspects of the ISM. Tatsuhiko
Hasegawa contributed to the chapter on chemical reactions in the ISM. Cements.
criticisms from several anonymous reviewers also helped improve the book. I want to
thank the many authors who kindly allow their figures or other published materials to
be used in the book. I also thank Orla Aaquist and Alexander Menshchikov for their
careful readings of earlier drafts. and Emily Wei for her help in preparing some of the
figures. The manuscript was proofread and checked by a number of students. including
Joanna Wong. Nico Koning, Rong Ying Wu. and Jo Hsin Chen. The production of
this book was professionally done by University Science Books. in particular Jane
Ellis and Mark Orig who handled the manuscript and the graphics respectively. I
thank Bruce Annbruster for his patience and continuous support. Especially, I want
to thank my wife Emily who tolerated my long working hours and frequent trips away
from home. Without her understanding and support. this work would not have been
possible. Finally, I would like to pay tribute to Gerhard Herzberg. whose contribution
to interstellar chemistry has been a great inspiratiOn to me and many others who work
in Canada.

Sun Kwok
Hong Kong. March 2006
1
The Interstellar Medium

The exiStence of interstellar matter was first inferred by the absence of stars in
certain dark patches of the Milky Way. The 1927 photographic atlas of the Milky
Way by E. E. Barnard included many dark clouds silhouetted against the background
starlight. Such dark patches are not due to a lack of stars in these regions but are the
result of starlight being blocked from View by intervening interstellar dust absorption.
Interstellar reddening. in which the colors of stars are modified as a result of selective
extinction of starlight by dust in the interstellar medium (ISM). provides further proof
for the presence of interstellar matter.
Interstellar matter can also be directly observed. The catalogue of nebulous
objects compiled by Messier in I784 contained two kinds of nebulae: those that are
made up of stars (e.g., the Andromeda nebula). which we now call galaxies or star
clusters; and gaseous objects (such as the Orion nebula). which are objects in the
ISM. Gaseous nebulae can be just regions of higher matter concentration in the ISM
(e.g.. H II regions), or represent material recently ejected from stars (e.g.. planetary
nebulae and supernova remnants).
How do we define interstellar matter? Stars are gaseous objects bound together
by gravitational self-attraction (Section 15.2). 50 at the fundamental level. stars are
not different from interstellar gaseous nebulae. However. the gravitational forces
inside stars are sufficiently strong that stars take on well—defined spherical shapes.
The concentration of high densities also provides sufficient opacity for stars to be
seen to have an apparent surface (the photosphere) that allows them to be viewed as
distinct entities. Most importantly. stars are self—luminous with energies generated by
thermonuclear reactiOns in the interior.
Interstellar clouds. to difi'erent degrees, also self-radiate. although not necessarily
at visible wavelengths. Clouds that are self-gravitating can take on well-defined
shapes. but others can be diffuse in appearance and often do not have well-defined
structures. Their low densities also imply that they are usually transparent (optically
thin. Section 2.6) at some Spectral regions, unlike stars. which are opaque at all
wavelengths.
Mosr stars (including the Sun) have stellar winds (Chapter 15) that eventu-
ally merge with the lSM, which, to a certain extent, is an extension of the stellar
atmosphere. This connection is more obvious for planetary nebulae. nova shells.
Wolf—Rayet star nebulae. and supernova remnants. Therefore. we should not view
2 The Interstellar Medium

interstellar matter in isolation. but instead it should be studied in the context of a

system in which stars play a crucial role.
What is the origin of interstellar matter? While galaxies contained a significant
amount of gaseous material when they formed. most of the primordial gas has been
used up to form Stars. The material in the present ISM has mostly been replenished
from stellar ejecta such as stellar winds or supernovae. The ISM therefore can be
considered as the result of mixing of ejecta from different generations of stars. and
the shaping and processing by subsequent radiative and mechanical events.

1.1 States of Matter in the ISM

Because of high temperatures. matter inside stars is primarily in an ionized state.

where atoms have loat one or more of their electrons. The ISM, on the other hand.
has a wide variety of temperature conditions. and almost all states of matter (ioniud,
neutral atomic, molecular, and solid state. with the exception of liquid) are present.
Since optical astronomy was the first observational technique to be developed, highly
excited atomic and ionic lines originating from high (~104 K) temperature environ-
ments were the first to be detected (Chapter 5). After the ionized component. the
molecular State was the next to be discovered as the result of molecular electronic
transitions observed in absorption against background stars (Section 7.6). The effect
of stellar reddening (Section 10.1) and the existence of dark clouds also suggested
the presence of absorbing material in a solid form in the ISM. The development of
radio astronomy in the l9505 led to the detection of the l. = 2| cm hyperfine transi-
tion of the hydrogen atom (Section 5.4.l) and demonstrated the wide distribution of
atomic hydrogen in the Galaxy. 1n the late 1960s. radio receivers of higher frequen-
cies became available and the rotational lines of molecules were detected at millimeter
wavelengths (Section 7.4). Vibrational transitions of molecules occur generally in the
near infrared, and vibrational bands of simple molecules were widely observed by
1980 (Section 7.5). The advent of infrared detection technology also led to the dis-
covery of continuous emission from solid-state substances (dust grains) in the ISM
(Section 10.3). The detection of neutral heavy atoms in low temperature environments
is more difficult because the low-lying energy states that are likely to be excited have
small energy separations and the transitions lie in the far infrared or submillimeter
(submm) parts of the electromagnetic spectrum. Demanding technologies, combined
with an opaque Earth atmosphere in this spectral region. are the reasons why the neu-
tral state of many common atomic species (e.g., carbon and oxygen) were detected
only after the deployment of infrared telescopes in high-flying aircraft (Section 5.3).
The opening of all specual observing windows by the placing of telescopes in
Earth-orbiting spacecraft has allowed a comprehensive study of the ISM. Most elec-
tronic transitions of atoms and ions occur in the ultraviolet and can now be observed
by ultraviolet telescopes (Section 5.I). The diffuse interstellar clouds excited to high
temperature by high-velocity shocks have been detected as a result of their continu-
ous emission in the X-ray region (Chapter 16). The greenhouse gas molecules (cg,
H20. C02. CH4). which are responsible for the opacity of the Earth's atmosphere and
 [.2 Inremrrr'nns bem'een Stars and rhe ISM 3

therefore impossible to observe from ground-based observatories. have been detected

by space-based far—infrared and submm telescopes. As the sensitivities of detecting
instruments continue to improve and the spectral coverage continues to widen. large
complex molecules (many of them organic) have been discovered by infrared and
millimeter observations. The chemical reactions that lead to the formation of such
large molecules will provide invaluable clues to the question of the origin of life.
The studies of the atomic. molecular, and solid-state components of the ISM also
serve as useful probes to the physical conditions of the ISM. giving us measurements
of the density. temperature. and kinematics of interstellar clouds. Some of the molec-
ular and solid-state materials are preserved in primitive solar system objects such as
meteOrites and comets. Although mosr of our knowledge of the [SM is gained through
remote observations. the possibility of physically examining meteorites or interplan-
etary dust in a laboratory provides an alternate avenue for studying the content of
interstellar matter (Section I15).
At the beginning of the twenty-first century. we are witnessing the golden age of
interstellar medium research. In this book. we will cover all the constituents of the
ISM. discuss how they can be excited under interstellar conditions. and with what
physical mechanisms they can radiate and be observed with ground-based or space-
based telescopes.

1.2 Interactions between Stars and the ISM

Stars. with thermonuclear burning in their interiors. are the energy source of almost all
the phenomena observed in the interstellar medium. The only other minor contributor
is the cosmic background radiation. Stellar energy is transferred to the ISM in two
ways: radiatively and mechanically. Diluted starlight intercepted by interstellar gas
and dust is responsible for the excitation of interstellar matter above the minimum
excitation provided by the cosmic background 2.7-K radiation. In addition to photons.
stars also eject matter in the form of stellar winds (Sections l5.6 and l5.7). and
occasionally by violent events such as supernova explosions (Section I62). Although
neutrinos are also produced by stars. they are believed to pass through the ISM without
much effect because of the small cross section of neutrino—baryonllepton interaction.
Besides energy exchange. another effect of stellar influence on fire ISM is chemi-
cal enrichment. All the heavy elements and much of the helium present in the Universe
today were produced by Stellar nucleosynthesis. These heavy elements are deposited
in the ISM by stellar winds and supernovae. thereby gradually enriching the metal
content of the Galaxy.
Our current understanding of single star evolution and nucleosynthesis is sum-
marized in Table 1.]. The different stages of nuclear burning that can occur in a star
are primarily a function of its initial mass. Whether a star can go throngh to anorher
phase of nuclear burning is dependent on the end product from the previous phase.
Mass loss on the surface can deplete the envelope. and therefore limit the mass of the
end product. terminating the evolution. The producrs of nuclear hunting in the core are
4 The Interstellar Medium

Table 1.1
The evolution of single stars and the enrichment of the ISM

Mass range Nuclear processes End product ISM enn'chment

M 5 0.08 MiB no H ignition brown dwarfs —

0.08 < HIM?) < 0.5 H core burning He white dwarfs --—
no He ignition
0.5 < MIME) < 2.2 ignite He degenerately C—O white dwarfs He. ”N. .r-process
in the core elements
2.2 < MIM,D < ~ 3 ignite He C—O white dwarfs He. C. I3C. "0.
nondegenerately s-process elements
8 < MIME < ~lO—IZ ignite C neutron stars He
nondegenerately
l0-12 c HMO < ~ 40 supernovae before neutron stars or black 0. Ne. Mg. Si. 5, Ar.
H depletion in the holes Ca. r-proeess elements
envelope
40<MIM19<~100 supernovae after WR neutron stars or black 0. Ne. Mg. Si. S. Ar.
phase holes Ca. r-prooess elements
I60
M :- l00M.;; 0 bunting after He “0116
exhaustion

brought to the surface through convective processes. These elements are then returned
to the ISM through stellar winds 0r explosive events.
Because of the initial mass function, stars in the 3rd and 4th rows ofTable l. I rep-
resent 95% of the evolved stars in the Milky Way Galaxy and are therefore mainly re-
sponsible for the enrichment of the ISM. The nuclear-processed materials are ejected
in the form of a stellar wind during the asymptotic giant branch (AGB) (Section 5.7).
Theoretically. C could be ignited degenerately in the core. but AGB mass loss invari—
ably depletes the H envelope before the core grows to the Chandrasekhar limit. so this
never occurs. at least not in the Milky Way at present epoch. Carbon ignition under
degenerate conditions may occur in an earlier generation of metal-poor stars when
mass loss was less efficient.
For massive stars (stars in rows 5-? of Table LI), 2 series of elements can be
ignited after C. leading to the formation of an iron (Fe) core. In addition to the
supernova explosion in the end, these stars also enrich the ISM through stellar winds
during the main sequence (0. B supergiants) and Wolf-Rayet phases (Section 15.6).
Therefore the present distribution of elemental abundance reflects the nucleosynthesis
history of previous generations of stars.
The chemical evolution of galaxies is the result of the star formation rate. the
initial mass function. the yield of processed material returned to the ISM. and other
physical processes such as galactic inflows and outflows. It should be emphasized that
 [.3 Chemical' Almrtdrrtrcer fit the ISM 5

our current understanding of stellar evolution (as summarized in Table l. I) represents

only the evolution of single stars in the Milky Way at current epoch. Since all first-
generation intermediate and high mass stars have already evolved in our own Galaxy.
we have no direct observational knowledge of their evolution. For example. different
metallicity may affect the mass loss rate. and therefore totally alter the mass range of
stars that can undergo certain nuclear burnings.
Supernovae are important not only in the enrichment of the ISM with r-proccss
elements. but also in the injection of mechanical energy into the lSM (Section I62).
Because of interstellar extinction tSection I0.I) and the low historical rate of super-
novae. the supernova rate in the Milky Way Galaxy is poorly known. However. from
the supernovae rate in nearby spiral galaxies. the rate of Type ll supernovae is about
1 per IOO years. This is roughly consistent with the theoretical expeCIatiOn from the
rate of evolution of massive stars (Table LI).
Supemovac Ia and lb are the results of binary star evolution. and their rates
are approximately 0.3 and 0.4 per 100 years. respectively. Type la supernovae can
arise from either merging of two electron degenerate C—0 white dwarfs. or mass
transfer from a red giant to a C—() white dwarf leading to a final mass exceeding the
Chandrasekhar limit. The origin of Type lb supernovae is unclear.

1.3 Chemical Abundances in the ISM

The collapse of the preasolar cloud gave rise to a global homogenization of material
available to form the Sun and planets. The resultant mix of the elements is referred
to as the cosmic abundances of the elements. A plot of the solar elemental abundance
as a function of atomic number is given in Figure H. in spite of the name "cos-
mic abundances." it should be remembered that the interstellar abundances are not
always the same as the solar values. and it is well known that there are elemental
abundance gradiean in the Galaxy. Even the solar values are subjected to uncertain-
ties in the atmospheric models (eg, l-D vs. 3-D. and hydrostatic vs. hydrodynamic).
line formation (Section 5.6). and the values of oscillator strengths (Section 5.6) used
to derive abundances from the photospheric lines. These uncertainties put the error
of solar abundance at ~ I090. A complementary method to determine the solar ele-
mental abundance is by the study of meteorites (Section l3.5.4). Although laboratory
abundance analysis of meteoritic material is not model dependent. elemental isotopes
are subject to fractionatiorr (Section 9.10). and volatile elements such as H, He. C. N.
0. Ne. and so on can be depleted in meteorites.
Since each element can be in ionic, atomic. molecular. or solid-state forms. an
accurate determination of the elemental abundance in the ISM requires observations
of the eletnent in all of the above forms. This is not easy even for the simplest
element H. A significant fraction of the interstellar H is in the molecular form. but
molecular hydrogen is extremely difficult to observe (Section 7.7. l). Although CO
is the most widely observed molecular species containing C. other oxides of C (e.g..
C03) and hydrocarbons are also present and need to be counted. Some C are in solid
6 The Interstellar Medium

:l:
ltmnmltHumilnmm.Inn...”[nmnnlmmml
:I:
a
loglo (Abundance relative to hydrogen)

é»

9
*o

LiBe
o—

‘llIIIII"lIIIIII'Ill_lllll‘lllllLll'lIl

IO 20 30 40
Atomic number

Flgure 1.!
The cosmic abundance of elements as a function of atomic number.

form (e.g.. C02 ice. Section 11.2.6; and carbonaceous compounds. Section 11.3.1).
The major transitions of ionic (C n) and atomic (C 1) forms of C lie in the infrared
and submillimeter wavelengths (Section 5.3). and their contributions to their total C
abundance have been ascertained only recently.
Although the chemistry of N is not as rich as that of C. its likely most abundant
molecular species N2 is difficult to observe due to a lack of a permanent electric-
dipole moment (Section 7.7). To estimate the N abundance. we have to rely on
the protonated ion N2H+ (Section 7.7.3) and other nitrogen-containing molecules
(NH3. HCN). Although N can also be in ices (e.g., NH3 ice) and N-containing side
groups can bepresent in amorphous carbonaceous grains (Section 1 1.3.2) andlor large
organic molecules (SectiOn [3.4). they are unlikely to contain a significant fraction
of interstellar N.
Like N, oxygen (0) is a difficult atom to study. The ground-state transitions
of atomic oxygen (0 I) lie in the far infrared (Section 5.3), and the major molec-
ular species H20 (Section 7.9.2) and 02 (Section 7.7.2) cannot be observed with
ground-based telescopes because of absorption by the same species in our aunosphere
 1.4 The Coupling between Interstellar Matter and Radiatiorr 7

“10% "i ' ‘ ' ' ‘ '

i fl I mm precipitablc water vapor J

m 1

E 60%} ll 4
q
.E“ _

s l
Emar l
i '1
mt _
l 1
0% l . . . L
O 200 400 600 500
Frequency (GHz)

Figure 1.2
Model of zenith atmospheric transmission at Mauna Kea for 1 mm precipitable water vapor. Even
under such dry conditions at a very high sue. the terrestrial atmosphere is still opaque In much of
the submillimeter wavelengths due to pressure-broadened transitions of water and molecular oxygen.
[Data from the Callech Submillimeter Observatory.)

(Fig. 1.2). Oxygen-based molecules generally have c0mplicated rotational energy

structures and their abundances are therefore spread over many different levels. mak-
ing individual rotational transitions weak and difficult to detect (Section 9.1). In the
solid state. 0 atoms are present in ices (H20. C0, C02, etc., Section 1 1.2.6) as wall
as in grains. in particular in the form of amorphous silicates (Section 1 l.‘2.l).

1.4 The Coupling between Interstellar Matter and Radiation

Other than the 2.7-K cosmic background radiation. the radiation field in the [SM is
dominated by diffuse starlight. in particular in the visible and ultraviolet wavelengths.
Thermal radiation from solid-state particles (dust) is the main contributor to radiation
in the mid and far infrared (Fig. l.3). In the radio wavelengths, thermal and nonther-
mal radiation from ionized gas gradually wins over the Rayleigh—Jeans tail of dust
E The Interstellar Medium

' 77 , T I fir l7 I a ‘li fi' I I I

2 C n (157 pm) i

l0.0 _- __
3 ' I
6 .
s 1
:~ 4i —
(rm 3 _ _

E . .
o 2_ Dust emissmn i
25"
o —
g 1-0 . Cosmic background radiation ‘-
5':- a- ;
6
5 l- 1
4_ -
3 _

2 _

O l I . - . . . . . . g 4 . . .
' I01 2 3 4 s e 1' s '03 2 3 4 5 6

Wavelength (,urn)

Figure 1.3
The integrated spectrum of the galactic plane as observed by the Cosmic Background Explorer
(CORE) satellite. Other than the cosmic background radiation. which is seen over the whole sky. the
ISM shows strong continuum emission from cool dust of a temperature of ~ 20 K. A line due to
ionized carbon is also prevalent on the galactic plane.

radiation. Besides localized regions of supernova remnants, very high-temperature

diffuse gas created by mechanical heating is the main source of X-ray radiation in
the ISM.
The first step in the coupling between interstellar radiation and matter is the
absorption of starlight by gas (Section 4.3) and dust (Section 10.2). Diffuse starlight
in the ultraviolet is absorbed by neutral H and He, resulting in the ionization of these
species in the surroundings of hot stars. The ejection of electrons as the result of
the absorption of Starlight is one of the major heating mechanisms of interstellar gas
(Section 6.5). The ionized component can cool itself in a variety of ways. including
the collisional excitation of heavy atoms and ions and the subsequent self-radiation
by these species (Section 5.12). the collisional heating of dust grains. and free—free
radiation through electron—proton encounters (Section 6.3).
Since most stars have temperatures in the woo-30.000 K range. visible photons
represent the major fraction of radiative output frOm stars. Since visible photons do
 1.5 Emission Nebulae and the Ionized Component of the iSM 9

not have sufficient energy to excite H in the ground state. they pass through the
ISM without much hindrance from the gas component of the Galaxy. Interstellar
dust particles, typically of submicron size, are macroscopic objects to the visible
photons and can absorb diffuse starlight efficiently. The absorption of starlight raises
the temperature of the grains ro 10—100 K (depending on their distance to stars),
which is balanced by cooling via self-radiating in the mid and far infrared (Section
10.3). The molecular component of the ISM can absorb these infrared photons through
the excitation of their vibrational energy levels (Section 7.5). Moleeules can also
be excited by collisions with gas that is heated by electrons ejected from grains.
When these excited molecules cascade to lower energy levels. they emit a series of
vibrational and rotational line radiation at millimeter and submillimeter wavelengths.
Although some of this line radiation can be reabsorbed by neigboring molecules, most
of the submillimeter radiation escapes from the ISM and the Galaxy.
Many common atoms and ions have lowilying fine-sanctum energy states (Sec-
tion 5.3) that can be excited by collisions with low-temperature electrons, such as
those released from grains through the photoelectric effect (Section l0.9). These in—
frared fine-structure lines can easily escape from the Galaxy and represent a source
ofcooling of the ISM (Fig. 1.3).
Although stars are the dominant energy sources in galaxies. interstellar matter
can transform the stellar radiation into radiation in other parts of the electromagnetic
spectrum, via both line and continuum processes. When viewed externally. galaxies
are more than just a summation of point sources of visible light. They also contain
extended regions of diffuse matter radiating from radio to infrared to X-ray wave—
lengths. Consequently. interstellar matter makes galaxies much more interesting
objects.
While much of the present interstellar matter was ejected from stars some time
in the past, it also provides the material from which new stars are formed. Before
interstellar clouds can collapse to form new stars, they first have to reduce their
thermal content through cooling. Many molecules in interstellar clouds have low-
lying energy states that are easily excited by collisions under low-density conditions
(Section 9.3). Spontaneous radiation from these excited levels removes kinetic energy
from interstellar clouds. allowing them to cool. The existence of molecules. formed
through various chemical processes either in the gas phase or on grain surfaces
(Chapter I4), is essential in the formation of new generations of stars. Therefore
the study of interstellar chemistry is closely tied to the physics of star formation.
and the physics and chemistry of the interstellar medium are highly dependent on
each other.

1.5 Emission Nebulae and the Ionized Component of the ISM

The wide presence of ionized gas clouds in the Milky Way Galaxy was first recog-
nized through photographic surveys in regions near hot stars. The observation of the
dispersion of pulsar signals by free electrons in the ISM further confirms that ion-
ized gas is a pervasive component of the ISM. Since ionized gas clouds manifest
themselves through line (e.g.. H recombination lines. Section 5.11) or continuum
10 The Interstellar Medium

radiation (e.g.. free—free radiation. Section 6.3). they can be efficiently identified in
emission—line (e.g.. Hot) or radio surveys. Since the National Geographic Society/
Palomar Obsen’ntory Sky Survey (POSS) red plates also include the Ho line in the
bandpass. many emission nebulae can be seen. Modern CCD detectors (Section 3.2.1)
have linear responses that allow for digital subtraction of continuum images from
their correspoading Hat images. Consequently. narrow-band imaging surveys are ex—
tremely efficient in identifying ionized clouds in our Galaxy. Examples of the recent
Ha surveys include the Southern Ha Sky SurveyArias (SHASSA, Fig. 1.4), which cov-
ers the entire southern sky up to declination of +15”. and the corresponding Virginia
Tech Spectral-Line Survev in the nor-them hemisphere.
Galactic nebulae that self-radiate in the visible are called emission nebulae.
"They are identified either as red nebulous objects in sky surveys (e.g.. the Sharpless
catalogue. which consists of mostly diffuse nebulae). objective prism or emission-
line surveys (e.g.. the Hat surveys of Lick Observatory). or radio surveys (e.g.. the
Westerhout catalogue). 0n smaller scales. Hot surveys with high angular resrrlution
can identify small. individual emission nebulae. For example, the Anglo-Australian
Obsen'amrjv/UK Schmidt Telescope Sttn’e)‘. with an angular resolution of ~ 1” and
covering an ~ 20°-wide region of the southern galactic plane. has discovered many
new emission nebulae.
Examples of emission nebulae include planetary nebulae. supemova remnants.
and diffuse nebulae. Planetary nebulae and supernova remnants are producrs of stellar
evolution. consisting of either gaseous material that has been ejected or interstellar
material that has been swept up by the ejecta (Sections I64 and 16.2). Both planetary
nebulae and supernova remnants have Well-defined morphologies (often shell-like
and sometimes bipolar). and can be associated with a single cenLtal star. Diffuse
nebulae (also called H II regions) are distinguished frOm the above two by their fuzzy
appearances. and are associated with sites of star formation. They are often found in
the vicinity of molecular clouds (Section l.7). These diffuse nebulae represent the
portions of the molecular clouds that have been photoionized by newborn massive
stars. They are therefore confined to the plane of our Galaxy. The spiral arms of
galaxies are often outlined by large numbers of diffuse nebulae.
Art emission nebula derives its energy from one or more embedded stars through
radiative or mechanical interactions. Diffuse and planetary nebulae rely primarily on
the radiative output of the central stars. whereas supernova remnants are powered
by the mechanical energy released in the supernova explosion (Section [6.2). Stellar
photons with energy over the Lyman limit (13.6 eV) can be absorbed by H. taking
it to an ionized state (Section 4.3). The subsequent recombination between the free
protons and electrons (Section 4.5) and decays from the excited states will generate
series of line radiation (Section 5.11). Collisional excitation by electrons with the
heavy elements can excite the atoms to a higher state. which subsequently undergo
radiative decay (Seetion 5.12). These recombination and collisionally excited lines
are responsible for the rich emission-line spectrum seen in the visible. The most
prominent lines in emission nebulae are the red Her line at 6563 A. and the green
lines of [O m] at 4959 and 5007 A. The interactions between the free prorons and
electrons can also generate thertnal radio radiation (Section 6.3).
ll
[.5 Emission Nebula: and the ham".2!(1 Component of the [SM

3&2 .n: (him .53 .E .o 3530 E2: 29 2: Ho EEEEou sonEE omen—E 2: ._o
222:; 2: mEBcfi Esra—:03 atom—am E Enema.“— zvtzw bi. at E353. 05 E 3523 «gang 3: caoflfinwégcscou 2: no u_.uv.oE d.
E 23E
12 The Interstellar Medium

Diffuse nebulae are much larger in size (tens of parsecs) and more massive
(101—103 M0) than planetary nebulae (10"! pc in size and ID" Me in mass).
Diffuse nebulae are also subdivided based on their sizes as ultraeompact H II regions
(size under 0.1 pc). compact H rt regions (0.1—! pc). "normal" H II regions (101
pc). and giant H ii regions (> I01 pc). The compact and ultracompacr H rt regions
are particularly prone to confusion with planetary nebulae. They usually can be
distinguished by the temperature of the associated dust components: the dust grains
in planetary nebulae are generally hotter (Td ~100—150 K) than those in H tr regions
(Td < IOU K). The exciting stars of H u regions are main sequence stars and therefore
have temperatures of no higher than 50,000 K. However. central stars of planetary
nebulae are H-shell burning stars and can have temperatures as high as 250.000 K.
The differences in the central star temperatures. and. consequently. the energy of
the photons available for photoionization. result in qualitative differences in their
spectra. For example. the recombination lines of ionized He (He u) are uSually seen
in planetary nebulae and rarely in H it regions. With less energetic photons available.
0 atoms in H II regions are mostly in the singly ionized state and the [0 III] to Ha
ratios are much lower in H II regions than in planetary nebulae.

1.6 Reflection Nebulae

In contrast to emission nebulae. reflection nebulae do not shine on their own in the
visible. Their nebular structure is derived from starlight scattered off dust grains in
the nebulae (Section 10.5). As a result, the Optical spectrum of a reflection nebula
is made up of the continuous spectrum of the illuminating stars. However. the color
of the reflection nebulae is often bluer than the stellar spectrum because the dust
particles scatter more efficiently in the blue (Section 10.1). The best-known example
of reflection nebulae is the Pleiades reflection nebula. which is illuminated by the
brightest stars in the Pleiades cluster.
Reflection nebulae are often found near sites of recent star formation. since yOung
stars illuminate the dark clouds from which they are formed. Typical reflection nebulae
have sizes of 0.] 1 pc. with densities of ~l0“ atoms per cma. The central stars are
B spectral type or later and are not hot enough to photoionize the nebula. The Trifid
nebula (M20) is an example of an object that is part emission and part reflection
nebula. In a color photograph. the red pan of the nebula is an emission nebula due to
Ho emission. whereas the blue part is a reflection nebula due to scattering.
Reflection nebulae are also found in the surroundings of evolved stars. for ex-
ample. dui'ing the short evolutionary stage between the end of the asymptotic giant
branch (AGB) and planetary nebulae (Fig. 1.5). In this case. the circumstellar dust
was ejected during the AGB phase and is illuminated when the central star evolves to
an earlier spectral type.
Related to reflection nebula is the phenomenon of diffuse galactic light due to
scattering of the general interstellar radiation field by interstellar dust. At low galactic
latitudes. the diffuse galactic light can account for as much as 20% of the overall
visible glow of the Milky Way.
 1.6 Reflection Nebulae 13

Figure 1.5
An example of a reflection nebula. This is a Hubble Space Telescope (HST) Wide Field
Planetary Camera (WFPC'Z) V‘band image of the Egg nebula (AFGL2688). The bipolar lobes
are the result of starlight scattered by dust in the circumstellar torus-like envelope.

Molecular hydrogen in reflection nebulae can undergo fluorescent emission in the

infrared as the result of absorption of UV photons (Section 7.7.l). In the reflection
nebulae around evolved stars, the excitation of molecular hydrogen is more often due
to shock heating as newly developed fast outflows push through the remnant AGB
envelope.
Reflection nebulae serve as a laboratory for the study of interstellar grains. From
the surface brightness distributions of reflection nebulae, one can derive the scattering
properties of the grains, including albedo and phase function (Section 10.2). From
these preperties. one can infer the size and composition of the dust grains.
The energy carried by stellar photons that are absorbed by the dust in reflection
nebulae are reemitted either as [henna] radiation in the far infrared (Section 10.3) or
14 The Interstellar Medium

as photoluminescence radiation in the visible (Section 11.2.7). The effect of photo-

luminescence is observed in the form of extended red emission (Section 12.4) and
can be observed in reflection nebulae as well as the diffuse ISM.

1.7 Dark Clouds and Molecular Clouds

In contrast to emission and reflection nebulae. dark clouds manifest themselves by the
absence of visible light. Their existence can be inferred through the exercise of star
counts. When a region of the sky has far lower stellar densities than the neigboring
areas, it is assumed that absorption by a foreground dust cloud is responsible. The gas
temperatures in dark clouds (estimated from molecular line studies; see Section 9.3)
are typically [0—20 K. Such low temperatures suggest that there are no strong central
heating sources inside the clouds. and their temperatures are maintained primarily by
external heating from nearby stars or cosmic rays.
On a smaller scale. there are compact. dense clouds known as Bok globules. They
are often spherical in shape and have densities higher than dark clouds.
Molecular clouds that are bright in the infrared and molecular-line emissions
are called giant molecular clauds. Their dust and gas temperatures, inferred from
infrared continuum and molecular-line emissions, respectively, are in the range of 50
to 100 K. Such high temperatures suggest that there must be internal heating sources
inside the cloud. These internal sources can be identified by near-infrared imaging
and are believed to be newly formed massive (OB) stars. The inferred masses (103—
106 M9) of giant molecular clouds suggest that they are not gravitationally stable.
and kinematic studies using molecular lines confirm that many are in the process of
gravitational collapse (Section 15.8). Giant molecular clouds are therefore excellent
objects to study the formation process of massive stars.
The collapse of giant molecular clouds leads to the formation of hot cores. which
have typical temperatures of ~l00—300 K and densities of ~10.Jl cm 3. Given such
physical conditions. hot cores are the mosr chemically rich sites (Chapter 14). The
best-studied examples of hot cores are Sgr B2. Orion Molecular Cloud—I (OMC- l ).
G34.3+0.15. and W3. From dynamical calculations. the lifetimes of hot cores are
estimated to be ~105 yr (Section 15.4).

1.8 Diffuse Interstellar Clouds and Infrared Cirrus

Unlike molecular clouds or emission nebulae. diffuse interstellar clouds lack a defi-
nite morphology and are semitransparent in the visible (AV ~ 1. Section 10.1). Being
exposed to starlight. the clouds are often in atomic form. and can be traced by the
A2l-cm H line. In the inner regions where the gas is shielded from starlight. simple
molecules can form. The first molecules detected in diffuse clouds are H1, HD, OH.
and C0 through their absorption lines in the UV, for example. by the Copernicus satel—
lite. Sometimes the term “translucent clouds" is used to refer to the class of interstellar
clouds between diffuse and molecular clouds (Av ~ 2—5). Molecules in translucent
clouds. in addition to being able to he observed through their absorption-line spectra.
 1.8 Drfihse Interstellar Clouds and Infrared Cirrus 15

can also be studied in emission with millimeter—wave techniques. At high galactic

latitudes. diffuse clouds are exposed to a smaller amount of UV radiation because
most hot (early-type) stars are concentrated on the galactic plane. As a result. these
high-latitude clouds have a diil'erent chemisu‘y than diffuse or translucent clouds.
Studies of diffuse and translucent clouds receive a great boost from recent de-
velopments in high-resolution spectroscopic observations from satellites. as with the
Space Telescope Imaging Spectrograph (STIS) of the Hubble Space Telescope and
the Far Ultraviolet Spectroscopic Explorer (FUSE). The abundance and physical en-
vironment of a large number of atomic and molecular Species (e.g.. C t. N t. 0 t.
C0. H2) can be measured through absorption spectroscopy against background stars
(Section 5. IB).
Dust grains in diffuse clouds absorb diffuse starlight in the general ISM and remit
the energy in the infrared. Figure 1.6 shows the spectrum of dust emission in diffuse
clouds. expressed in units of intensity per H. This is a broad far-infrared component

Ill—Ill I [rtltII I l' IIIIIYI

Observed emission from interStellar dust

lO'”
vlvaH (erg s" sr' H")

IR t I_ I I I l_|_l_|_l l I l l ll_1_l l I I
10'”
1000 500 300200 100 50 30 20 to S 3
1mm)
Figure 1.6
Infrared emission from diffuse interstellar dust clouds. The observed inlensities per H atom are
taken from IRAS (crosses). COBB FJRAS (squares). CODE DIRBE (diamonds). and Japan's
Infrared Telescope in Space (HITS. solid line) (from Dmine 2033. Encyclopedia ofAstronomy
and Astrophysics. Institute of Physics. p. 1263).
[6 The Interstellar Medittrtt

l .i'i‘lflll

flit iii“?

I‘iI Hut] 7

U .351?

gimme .‘

ease .
-D_..?I;tt"t I

I 01359

gee-ea

11.32am». Mm: (tiamx.qts.wfitaste tartan

Figure 1.1
The dil't'use nature or an interstellar dust cloud can be seen in this B-um image or M l6 taken during
the Galactic [argues Inflated Mill-Plane Surrey Et‘tram'dr'naite {GUMPSE} using the Infrared An'ay
Camera of the Spluer Space Telescope. image was created using data provided by Ed Churchwell
and the GLIMPSE team.

peaking at ~ I40 am. as well as several strong emission features due to aromatic
compounds (Section l2.l) in the 3—!5 um region. The peak wavelength of the far-
inl'rared component suggests a dust temperature of ~ 20 K, which is consistent with
grain sizes of 0.01—0.33 tun under thermodynamic equilibrium. The short-wavelength
component. h0wever. implies the presence of a dust component with much higher
temperatures. possiny originating from very small grains. The existence of a dif-
fuse interstellar dust cloud can be seen in the galactic plane survey of the Spike:-
Space Telescope. Figure L? shows the S-um image of the H II region M16. At this
wavelength. the light is completely due to dust emission. Several low-density bubbles
cleared out the fast stellar winds. as can be seen in the nebulae (Section l6.3).
The first evidence for "cinus" c10uds was the observatiOn of faint reflection neb-
ulnsity at high galactic latitude. Their existence was confirmed through the detection
of infrared emission by the Infrared Astronomical Satellite (IRAS). The fact that such
diffuse clouds are detected at the l2- and 25-11 m bands suggests that the grain tem-
perature must be high (IOU-500 K). Due to the lack ofheating sources at high galactic
 l. 10 Multiple Phases of the ISM l'l'

latitudes. these grains cannot be in thermodynamic equilibrium. One possible expla—

nation is that these are very small grains that are heated by single UV phot0ns, leading
to high transient temperatures (SectiOn 10.7). It is estimated that approximately 20%
of the sky is covered by infrared cirrus. Broadband photometry and spectroscopy of
diffuse, high-latitude cirrus clouds reveal an optical emission over scattered starlight
and diffuse galactic light. This component is similar to the extended red emission seen
in reflection nebulae (Section [2.4), and is the consequence of photoluminescence
(Section l 1.2.?) from ambient galactic light. The integrated intensity of this emission
component is ~ 30% of that of the scattered starlight in these diffuse clouds.
Large-scale CO surveys have revealed numerous small molecular clouds at high
galactic latitudes. It is likely that these are local clouds in the proximity of the Sun.
The typical masses of these clouds are several orders of magnitude smaller than those
of giant molecular clouds.

1.9 Hot Gas and Galactic Corona

The possible existence of a hot galactic corona was first discussed in 1956 by Lyman
Spitzer. He predicted that such a hot component of the ISM can be observed by the
detection of the resonance doublet absorption lines of Li-like ions of 0 VI, N v. and
C iv. For example. the ionization potential for 0 v to 0 v1 is 113.9 eV. corresponding to
a wavelength of 109 A. Since the interstellar background radiation in the far ultraviolet
is very low (Section 4.7). it is unlikely that 0 Vi can be produced by photoionization.
Therefore, the detection of 0 v1 requires collisional ionization and by implication the
existence of hot gas. Assuming equlibrium in collisional ionization, the ions 0 VI,
N v. and C 1v will have peak abundances at ~10S K.
The 0 Vi line was first detected in absorption by the Copernicus satellite. followed
by the detection of N V. C iv. and Si IV by the International Ultraviolet Explorer
tl’UEJ. The Far Ultraviolet Spectroscopic Explorer (FUSE), launched in 1999, was
designed to cover the spectral region from 905 to l 187 A, and is therefore particularly
suited to observe the strong resonance lines of C 111. 0 Vi, and S v] (Section 5. I). By
measuring the column densities of 0 v1 against extragalactic background sources,
FUSE was able to determine the 0 v1 scale height in the hot galactic corona to be
w 3 kpc. Similar values of 4—5 kpc for N v, C iv. and Si iv have also been found by
[UPS and Hubble Space Telescope (HST) observations.
What is the origin of hot gas in the galactic halo? Mechanical heating by shock
waves is the most likely source for bringing the gas to such high temperatures (see
Chapter l6). Correlated supernova explosions in DB star associations can create super
bubbles of hot gas. which expand and break out of the plane of the Galaxy and
transport the hot gas to the halo.

1.10 Multiple Phases of the ISM

The preceding sections show clearly that the ISM is a diverse environment. Through
the application of a variety of observational techniques. the distribution of different
18 The Interstellar Medium

forms of interstellar matter can be mapped. Generally speaking, the discrete inter-
stellar clouds are concentrated in the spiral arms. and they occupy ~1—2% of the
interstellar volume. While most of the mass in the [SM is contained in the cold.
molecular component. most of the space may be occupied by a hot. ionized com-
ponent. More interestingly, the ISM also likely includes the transition phase of a
wann component. which can be either neutral or ionized. Evidence pointing to the
existence of a warm ionized component includes diffuse Ha emission (Fig. L4). high—
level radio recombination lines of hydrogen (Section SJ [.3]. and pulsar dispersion
measures. More recently, the far-infrared fine-structure line of ionized carbon (C+).
which has an ionization potential less than that of hydrogen (Section 5.3). has been
used as a tracer of the warm ionized component. The interface between the warm and
cold neutral components is defined by the photodissociation of molecules by diffuse
galactic starlight. and such photodissociation regions (PDRs) can be sites of active
chemical processes (Chapter 14). A summary of the physical characteristics of the
various phases of the ISM is given in Table 1.2. and a schematic representation of the
spatial relationship between these components is shown in Figure 1.8.

Table [.2
Interstellar medium components and their physical properties

Common Density ‘ State of Typical

ISM component designations T(K) (cm‘J) hydrogen r,’ diagnostics

Hot ionized Coronal gas I06 0.003 H+ l X-ray emission. UV

medium absorption
Warm ionized Diffuse ioniZed gas 10" > It] H+ 1 Optical. UV. IR. H a.
medium H II regions
Warm neutral lntercloud H l 8 at 103-104 0.l HD 0.1 El-cm emission
medium
Atomic cold Diffuse clouds I00 l0-100 H" + H2 ~ lo-J 2I-cm absorption. 3.4.
neutral medium urn absorption, UV
absorption
Molecular cold Molecular clouds. 0—50 I05—I05 l-l2 10-7—10-3 ExtinCtiOn. far-IR.
neutral medium dark clouds radio: CO. CS. NH].
H1C0. HCO"
Molecular hot Protostellarcolcs 100—300 2- l0“ H2 5 IO'8 Rovibrational
cores emission CH3CN,
CH30H. NH3. HCN.
$02

’ Density of H2 in molecular clouds and cores (11”,). otherwise density of H In").

' ionization Fraction (.r,).
Adapted from Wooden. Chart-icy. and Ehrenlreund 2005. in Camels ll. eds. M. FCSIIJIJ. H. U. Keller. and H. A. Weaver (University of
Arizona Press: Tucson).
 19
no Multiple Phase: ofthe [SM

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3:8. 33 Ea .EE—UE =53: Eco .EzauoE 35.0: :53 .5552: EB :53 45.69: 32:2 .3
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20 The Interstellar Medium

The modern study of the ISM goes beyond the physics of the interaction between
radiation and atoms. and extends into the realm of chemiSUy. Chemistry of the ISM
includes not only the traditional chemical reactions of interchange of atoms between
molecules in the gas phase. but also chemical reactions on grain surfaces (Section
14.3). The effect of chemistry can be seen through the absorption and emission of light
via rotations and vibrations of molecules. as well as through absorption, scattering.
and emission of light by solid-state particles. Although it is natural to assume that
chemical processes are confined to the dense and neutral phases of the ISM. the
discovery of infrared cirrus suggests that complex, organic compounds are distributed
throughout the Galaxy, even in the diffuse ISM.

1.11 Summary

The ISM is a fascinating subject to study because it encompasses a wide variety of

states of matter. and it manifests itself over the entire electromagnetic spectrum. At
the beginning of the twenty-first century, we finally possess many of the observational
means needed to explore the physical and chemical contents of the ISM. Our tradi-
tional view of the Galaxy has been dominated by the distribution of stars. Through
imaging surveys in the X-ray regions. Ha. infrared continuum. CO. H t. and radio
continuum, we can map out the distribution of all forms of matter in our Galaxy.
With spectroscopic techniques from radio to K-ray. we can probe the conditions of
atoms and molecules through their electronic. vibrational, and rotational transitions.
By making use of the radiation transfer and statistical equilibrium equations that we
will discuss in the next chapter. we can derive the physical conditions (density and
temperature) of the ISM from the observed line strengths. Most importantly. we can
obtain the relative abundance of matter in various forms. Take the case of carbon as an
example. 15 most of this element in ionized. atomic, molecular, or solid-state forms?
If a significant fraction is in molecular or solid-state forms. how much of it is in the
form of organic compounds?
The main emphasis of this book is on the physical and chemical processes that
occur in the ISM. Starting from the fundamental principles of atomic and molecular
physics. we discuss the radiative mechanisms that can result from these processes and
how the observed radiation can be interpreted to yield physical paramuers. As much as
possible. we uy to tie these theoretical concepts with observational results. especially
those obtained from space observations. Although the observational techniques of
imaging and photometry are covered in this book. spectroscopy takes a prominent
place because it is most closely related to the quantum processes under discussion.
2
Fundamental Concepts
ofRadiation

Astronomy differs from all other sciences in that it relies on passive observations of
the subjects to understand their nature. Most of the celestial objects are too far away
for active experimentation. Even for solar system objects. which can be reached by
spacecraft. experiments consist mainly of sample gathering. not manipulation. Unlike
experimental physics. chemistry. or biology where controlled experiments can be set
up to minimize or exclude certain variables, we have to acceptthe Universe as it is. Our
knowledge of the Universe is derived predominantly from the detection and analysis of
electromagnetic radiation. with the remainder derived from meteorites. interplanetary
dust. cosmic rays. neutrinos. and gravitational waves. Using information inherent
in the photons that we detect. and relying on our knowledge of the physics of the
interactions between radiation and matter. we deduce the state of matter and the
environment in which it resides.
For these reasons. the study of radiation and its interactions with matter is the
most fundamental aspect of astrophysics. Tire first step toward making astrOnomy a
quantitative science is to define and quantify concepts relating to radiation. Because
visual perception is the most important part of our senses, we can draw on our
everyday experience in building this foundation. Our vision can differentiate colors
and degrees of brightness as well as judge the direction of light. These are some of
the concepts that we need to quantify in the study of radiation.
Our vision also allows us to infer the existence of matter. Through touching. we
can tell that a rock is there. but not a cloud. However. we can visually infer that a
rock or a cloud is there because they obstruct or reflect background light. Therefore.
one of the ways we can perceive the existence of an object is through its opacity to
light (Section 2.6). Although we cannot see an object that is transparent (e.g.. air). we
can tell the existence of gaseous or microscopic material if it is self-radiating (e.g.. a
flame). The interaction between matter and radiation through absorption. reflection,
and emission is the main means by which we learn about objects in the Universe. The
reason why objects in our everyday lives have different colors is because objects
made up of different materials absorb, reflect. or emit light differently. With the
same principle. but using more precise measurements. we can determine the chemical
composition and physical environment of distant matter in the Universe.
21
22 Fundamental Concepts ofRadiation

2.1 Intensity
Let us consider a person standing in a room. Light is coming to us in all directions.
from lamps and fluorescent lights in the ceiling, from sunlight coming in from the
windows. and from reflected light from the walls and the floor. The brightness of light
is highest from directions of the lamps and the windows. and probably lowest from
below from the floor. In order to quantify the brightness of radiation perceived by this
observer, we would like to incorporate color. direction. and the rate of energy received
into a single eoucept. Color can be expressed quantitatively in either frequency (v) or
wavelength (1) units. which are related by v}. = c where c is the speed of light. The
rate of energy flow can be expressed as the amount of radiative energy passing through
a unit area per unit time. Let us shrink this person to a differential area element do.
which is located at the origin of the coordinate system as shown in Figure 2.1. The
directions of light can be described by angles (9. ¢) (Fig. 2.2). Consequently. we can
construct the concept of specific intensity as the limit in the following equation when
all the differential elements approach zero:

dE = fvda cos Bdwdv dt, (2.l)

where dE is the energy of radiation that passes through an area do within solid angle
dw. 9 is the angle between the normal of this area and the direction of light, dt is

dA

(-9 do)

dd
\_/ "'

Figure 2.1
11ie geometry of a beam of light passing through a unit area element do at an angle 0 w.r.t.
the normal of the receiving alert-tent da'.
 2.1 Intertrlry 23

--___,__”_-— ----.._
4"

-
... ________
—u.-___.—-__—--

Figuren
The solid angle element (the dark rectangular area) is given by dry = sin 9:19“: in the spherical
(r. 0. ‘33) coordinate system.

the time interval over which the energy dE is measured. d v is the frequency interval
(Fig. 2.1). In general. I” varies with position. direction, and time and has dimensions
erg cm": steredian'l Hz" 5".
We should note that the measurement of intensity refers to a point in space
(dor —> 0) of light coming from all directions. The angle 0 can go from 0 to r: from
the z axis. and ¢ can go from 0 to 21: on the J: — 3: plane. If we consider a ray of light
passing through two different areas do at position P andda‘ at position 1'” separated
by distance r. the amount of energy that passes through both do and da’ is

dE = luda cos dedv d!

dE’ = lada’ cos 6’dw’dv d: (2.2)

Since 4:» = da’ 005 97:3 and dw’ = do cos Glitz. and «”3 = dE’. we have

d ' ' ,
Ivdacosa(LEE—51)dvdr=lvdo’cosfl’( d ”:6 o )dudr
r r

1,, = 1;. (2.3)

24 Fundamental Concepts of Radiation

Therefore. the specific intensity is independent of distance. The solar disk will appear
smaller in angular size from Mars than from Earth. but the observed intensity (or
surface brightness) would appear to be the same.
Specific intensity can be measured for all objects that subtend a finite angle from
the point of view of tile observer. This includes most objects in our everyday life.
and in the astronomical setting. the Sun. the Moon. galactic nebulae. galaxies. and
so on. For this reason, the term “surface brightness" is sometimes also used to refer
to intensity.I Most stars. however. have angular sizes too small to be measured by
conventional telescopes (spatially unresolved). Consequently. the specific intensities
of stars are generally not measurable.
Specific intensifies can also be defined as per wavelength interval as I... The two
definitions of specific intensities are related by

d1
I=I
v —-.
lldvl ( 2.4 )

leading to the conversion formula

pl. = MA. (2.5)

Although we will primarily use the frequency units in this book. equivalent wavelength-
based expressions can be easily derived using eq. 2.5.
Integrated ancestry (I) is defined as the intensity over all wavelengths {or fre-
quencies)
DC 09
1:! ludv =1- del. (2.6)
0 0

2.2 Flux

Although most visual objects in our everyday life have relatively large angular extents.
most astronomical sources are distant and have small angular sizes. It would be useful
to devise another concept that measures the perceived total brightness of astronomical
sources. Mathematically. we define flux as the total intensity passing through do
summed over a solid angle d9 of the source:
JD
Fu = f 1. cos em. (2.7)

l. [n radio astronomy. intensity is often expressed in terms of brightness temperature. which has
units of degrees Kelvin (Section 3.1.2).
 2.2 Flux 25

The net flux of radiation at a point in space from all directions (Fig. 2.2) is
therefore .
Zr! 11'
n=L £1fiflhhflfl¢ am

The unit of F” is erg cm‘2 s‘le“'. In radio astronomy. the unit of Janslcy
(l Jy = 10-13 erg cm‘2 s‘I Hz'l) is also used. Integrated flux, the total amount of
radiative energy crossing a unit area per unit time. is given by
on CD

F=f nw=f am. am

0 0

For an isotropic radiation field where the intensity is not dependent on angle,
eq. 2.3 becomes
If

F, = 211' lv f cos 0 sin Odd

o
= n I, [sin2 0];

= O. (2.!0)
In an isotropic radiation field where every intensity element received is exactly
balanced by an opposite one, the net flux is zero.
For a nonisotropic radiation field, we can use the previous example of a person
standing in a room where he receives a high intensity of radiation from the ceiling
light. as well as low-intensity radiation from light reflected from the walls and the
floor. The net flux received is the summation of all these intensity elements over the
360“ angle and will be nonzero.
Now let us apply these concepts to the interstellar medium and consider our
material medium is a star or an interstellar cloud. Let us assign the origin of the
coordinate system to be a point on the radiating surface and assume that the surface
of the medium is infinite in extent on the x — y plane (Fig. 2.3). In this plane-parallel
geometry. all physical quantities are functions of the vertical coordinate z and angle 9
only and are independent of#5. the angle around the z axis on the x — y plane (Fig. 2.2).
From the point of view at the origin on the surface. the flux can be separated into two
components: one emerging from the medium (or outward. F") and one incident onto
the medium (or inward. F ‘), corresponding to 9 < rr/Z (above the Jr — 3; plane) or
9 > arr/2 (below the x — y plane). Specifically, the net flux is F = 1"" — F‘ where
117 n12
F+ =1 f 1 cos 6 sin 9d9d¢
ll 0
2x 11’
P" = -f f I 6059 sin 3d6d¢. (2.11)
0 If}?
26 Fundamental Concepts ofRadiation

la Emergent intensity

Figure 2.3
For a radiating medium (shaded in grey) in the plate—parallel geometry of infinite depth
(z —r —on). I and F are independent of¢ and are functions of z and 9 only. in this case.
the angle 9 is defined as the angle between the vertical axis 2 and the direction of light. The
emergent and incident intensities correspond to 0 < 6 < rr/Z and rr 2» 6 > 17/2. respectively.

For an isotropic radiation field.

1'12
F+=27rlf sin 9d(sin 0)
0
=11], (2.12)

the outward flux is therefore 11' times the intensity.

The separation of fluxes into inward and outward fluxes is of particular relevance
in a stellar atmosphere. For a star. the emergent (outward) flux from the star greatly
exceeds the incident (inward) flux that it receives from the interstellar radiation
field. In a plane-parallel atmosphere. the 9 = 11/2 plane neatly separates these two
components. Since F+ >> F ‘. the net flux at the stellar surface can be considered to
be equal to the emergent flux.
 2.2 Flu: 27

Flgure 2.4
A schematic diagram illustrating the relation between the emergent intensin from a star and the flux
as measured by an observer at distance D.

We should remember that the flux is defined for a specific reference point in
space. The relation between the flux at the stellar surface to the flux as received by
an observer on Earth (Fe) can be very difierent. The observed flux is given by the
sum of light rays I (a) over the maximum extent (amu) (see Fig. 2.4). The flux at the
position of the observer is

In “m
F9 =f f [(11) coscr sin adore”. (2.l3)
o o

where an,“ is the angle at which I is tangential to the surface of the star. Outside this
angle

am = sin"(R/D). (2.14)

1(a) is zero. The angle a is related to 9 by

a = Rsm(6 —a')
D . ( 2.l 5)
28 Fundamental Concepts ofRadiation

where D is the distance from Earth to the surface of the star. At large distances. at is
small and

tanasu “"19. (2.15)

D
From this relation, 3 change of variable from at to 9 can be made and the flux can be
obtained with an integration over 9 (from 0 to ir/2).
For a star with unifortn surface brightness (not dependent on angle 6). F"' = 7r]
(eq. 2.12). The intensity received by the observer 1 (tr) is therefore also not dependent
on the angle. Equation 2.13 then becomes
' 2 mu
Fe=2nlxM. (2.11)
Making use of eq. 2. l4, we have

Fe = rrl(R/D)2
= straw)? (2.15)
The observed flux therefore decreases as the inverse square of distance. This is
in contrast to intensity. which remains unchanged with distance. In our everyday
experience when we perceive an object getting fainter at greater distance, it is the
flux that we are obserVing.
The concept of flux is particularly relevant to stars. as most stars are not angularly
resolved and their specific intensities cannot be meaSured. Our perceived brightness
of stars corresponds to their flux. which decreases as the inverse square of distance.
Other than geometric dilution. flux is also attenuated by absorption (Section 2.6)
by the Earth's atmosphere. the interstellar medium. and the intergalactic medium.
While the effects of the Earth's atmosphere can be avoided by placing a detector
outside of the Earth's atmosphere. the effects of interstellar extinction (e.g.. in the far
ultraviolet; see Section 4.3) can be severe. Our ability to infer from the fluxes observed
at Earth the flux emergent from astronomical sources through the inverse-square law
is therefore always hampered by this uncertainty.

2.2.1 Power and Luminosity

Although the concept of flux is most commonly used as a measurement of brightness
for small objects. flux is also useful as a measure of the total energy output of an
object. Assuming that the radiation is entitled over all angles 0 < 0 < rr/2 equally
and is not preferentially beamed at us. the luminosity (L). or power. is given by

L =4JrDZF+. (2.19)
where D is the distance to the object. Luminosity is measured in units of erg s' '.
Since the emergent flux is almost always much larger than the incident flux
for stars and interstellar clouds and nebulae. we will assume F = F+ and omit the
superscript in the subsequent discussions.
 2.3 Moments of Intensity 29

2.3 Moments of Intensity

The concept of mean intensity (1”) is useful if we are interested only in the average
brightness at a certain point in space and are not concerned about the direction from
which the radiation comes. For example. the rate that a dust grain in an interstellar
cloud is heated is dependent on the intensity of radiation it receives from all (41:)
solid angles (Section 10.3.2). Similarly. the absorption of a photon by an atom is
also proportional to J (Section 5.5). Mathematically. 1,, can be defined as the aeroth
moment of specific intensity:

1,: I Iudw
I do)

I
= —— Indra. (2.20)
411'

For an isotropic radiation field. obviously J" = 1'”.

Over a time interval (1!. the total volume of light passing through do is cos 8 doc
dt. If we define the energy density u” as the amount of radiation energy per volume:

dE
d = —, 2.2]
it cos Hdcrc dtdv ( )

then from eqs. 2.] and 2.20, we can see that the concept of mean intensity is related
to radiation energy density:

4
u” = in. (2.22)
C

The first moment of intensity can be written as

L, 9d
H, = Iii (2.23)
I do:

and we can see that it is just another expression for flu:

H, = L. (2.24)
4n

Similarly. the second moment of intensity is defined as

I 2 9d
XI, = LEE—‘3. (2.25)
fdw
30 Fundamental Concept: ofRadiation

As in the case of integrated intensity.

all on

H=f ma=f ma
0 0
m no

K=j Kudv=f Kldl (2.26)

0 0

Since the momentum of a photon is given by E{c and pressure is the flux of
momentum. which is equivalent to force per unit area. radiation pressure can therefore
be expressed as

_ cosOdE/c dr
til” (2.27)
do

P=lflcos29dw (2.23)
I:

4
=1;- (2.29)
6

K is therefore related to the concept of radiation pressure.

For an isotropic radiation field. H = 0 (eq. 2.10) and
I 111' Jr
K=— f f cos2 9 sin 0d9d¢
4H 0 n

= U3. (2.30)

The radiation pressure in an isotropic radiation field is therefore

3:
=u/3. (2.31)

2.4 Thermodynamic Equilibrium vs. Steady State

In thermodynamic equilibrium. photons obey the Bose-Einstein distribution law and
the population density in the frequency interval 1: to v + dv (”1) at temperature T at
energyE=hvisgivenby

n 3n
= ______‘
" £5!er _ l
(2.32)

where the 3,, is the degeneracy of each energy. The number of states available in the
phase space is V4rrp2dp/h3, where V is the volume and p = Irv/c is the momenmm
of the photon. Therefore,
 2.4 Thermodynamic Equilibrium vs. Steady State 3!

4n vzdv
sudv= (‘3
. (2.33)

Since each photon has two possible states of polarization. the photon number
density is

13m)1 l
nu = T E’W/k—T—_1 (2.34)

and the corresponding energy density distribution (nu = unit 1:) is

arrhv3 I

Since blackbody radiation is also isotropic. the specific intensity of blackbody radia-
tion (3”) can be obtained from eq. 2.22:

3
Bu = 2'3. _1_. (2'35)
62 ehv/iT _ 1’

which is also referred to as the Planckfunction.

We note that the energy distribution is dependent on only one parameter. the
temperature. In order to be more precise. it is sometimes referred to as radiation
temperature (T3) or blackbody temperature.
For a system of noninteracting classical particles of mass rrr. if the frequency
of collisions is high enough. their velocity distribution is dependent only on one
parameter I], and is given by the Maxwellian distribution:

4 "I all 2 2 u]!-

[(11): 7:;- (fi) U 9"” I I. (2.37)
I:

Since 1} defines motion, it is referred to as the kinetic temperature. In order for an

ensemble of particles to achieve Maxwellian distribution. they have to effectively
exchange energy and momentum. and this is accomplished by interparticle collisions.

For quantum systems that have internal degrees of freedom. such as the move-
ment of an electron from one bound state to another, the relative population distribu-
tions of the internal states can also be described by one parameter 1"I in the form of
the Boltzmann equation:

fl = firearm. (2.33)
”r 8}
where n,- and n} are. respectively. the population of the upper and lower state. EU is
the energy separation between the two states. 3; and g}- are the degrees of degeneracy
of the two states. and T1 is called the excitation temperature.
32 Fundamental Concepts of Radiation

Expressed in terms of the number density in the ground state (In). the number
density of an excited state is

n, = flrile E'MT‘. (2.39)

8|
and the total number of atoms in all states is
(I;

N = ? E g); 51"“5. (2.40)

l
By defining the partition function as
m

Z=Zsre 5"”‘71. (2.41)

1
we can express the number density at each level as a function of the partition function

n, = NSE'e EN“. (2.42)

In high-density environments where collisional excitation and de-excitation dom-
inate the excitation of atoms and molecules. TJr in eq. 2.33 is the same as the kinetic
temperature 1}. Similarly, if the transitions are dominated by radiative processes, It“,
would be the same as TR.
In addition to excitation. collisions can also cause the ionization of an atom:

A,+e—>A“l+e+e. (2.43)

In this process of collisional ionization, the colliding electron loses part of its kinetic
energy to overcome the ionization potential EI to take the atom from the x ionization
state to the 1 + l ionization state. The reverse process,

Axil+e+e—>A,+e. (2.44)

is called recombination. In a high-density environment where ionization and recom-

bination are dominated by eqs. 2.43 and 2.44. respectively. the number densities of
ions in successive ionization states (nJr and up”) are given by the Saha equation:
33?.
"I = ( ”2 ) 2’ e511” (2.45)
n,+.n, 27mg” 22,+I '
where T is the kinetic temperature of the particles and ZJl and Z,“ are the partition
functions of the successive ionization states:
CD

2,. = Z g,e Ext/“K (2.46)

l'
 2.4 Themadynamic Equilibrium vs. Steady State 33

For a quantum sysrem with internal energy distributions obeying eqs. 2.38 and
2.45. and immersed in an external field of colliding panicles obeying eq. 2.37 and
a radiation field obeying eq. 2.36 where all temperatures have the same value. this
state is referred to as thennodynanric equilibrium. If all the preceding conditions are
satisfied except that the external radiation field is not Planclu'an. we refer to the state
of the system as being in local thennadynamr'c equilibrium (LTE).
In the terrestrial environment. where the density of the air is very high and
collisions between molecules are frequent. the temperature of macroscopic objects
settles at the kinetic temperature of the air (T ~ 300 K). When they radiate. their
emission spectrum will be governed by Planck’s law at the kinetic temperature. The
same high collisional rates also ensure that the excitation and ionization of atoms and
molecules are well described by the Boltzmann and Saha equations. respectively. In
stellar interiors or atmospheres. the radiation background is generally high enough
such that radiative processes also contribute to the excitation of atoms. In spite of
the fact that the excited states of hydrogen (H) have too high energies to be excited
by collisions from the ground state in stellar atmospheres, the electrons in H atoms
are distributed under perfect Boltzmann distribution because they are connected
by interlevel collisions. Once an excited state of H is populated by recombination
(Section 4.5), other excited states can be populated by collisions from this state.
therefore ensuring a Boltzmann distribution.
However. in the ISM where the density is low, we cannot assume that all energy
exchanges are dominated by collisional processes. Radiative processes begin to be
competitive. For example. the spontaneous emission rates of H are much faster than
the H-H collisional excitation rate in the ISM. and the population distribution of the
energy states of interstellar H is no longer related to the kinetic temperature. If we take
an extreme case of isolated atoms away from interstellar clouds and stars. absorption
of the cosmic background photons will be the main excitation process. The energy
distribution of the atoms will obey the Boltzmann distribution. but at a temperature
of 3 K. We can therefore no longer assume that the energy distributions of electrons.
atoms. or photons will be governed by a single temperature.
111 a system of randomly moving particles (e.g.. inside a gas cloud). the average
time between collisions is given by

I ~ —I I (2.47)
HUI)

where n is the number density of particles. cr is the cross secrion for interparticle
collisions, and u is the random velocity. If we consider the simplest possible case
and assume that cr is approximately given by the geometric cross section of an
atom (1- IO“" cm2) and in ~ lltnt s l. we can see that r is of the order of 1 yr for
n ~ I03 cm 3. This is short in comparison to other typical interstellar time scales
(e.g.. the dynamical time fer the collapse of an interstellar cloud; Section 15.4). In
the ISM. charged and neutral particles collide through a variety of ways. which allows
the Maxwellian distribution (eq. 2.37) to be established over short time scales.
34 Fundamental Concepts of Radiation

The radiation field in the ISM is far from thermodynamic equilibrium. in the
visible wavelengths, the interstellar radiation field is dominated by diluted starlight.
whereas in the infrared and submm regions. diffuse emissions from interstellar dust
represent the most important contribution. The excitation of atoms and molecules in
the [SM is determined by the radiative interactions (through absorption and stimulated
emissions) with this background radiation field. as well as by collisions with gas
particles. The excitation of atoms cannot be described by the kinetic temperature.
and they can depart greedy from the Boltzmann distribution. In fact. the population
distribution cannot be described by one parameter or one formula alone. This does not
mean. however, that die population distributions cannot be determined; it just means
that the LTE condition has to be relaxed and another assumption is needed. If we
assume that the population distribution is not changing with time. then the population
at each level j is govemed by the statistical equilibrium equation where the incoming
rate (RU) to each level is exactly balanced by the outgoing rate (Rn):

nJ- z le=anRkfl (2.43)

t it
where the population ofeach state (it 1-) adds up to a fixed sum N ofthe total population:

2 n}- = N. (2.49)
1'

When eq. 2.48 is satisfied. the system is said to be in a steady state.

2.5 Blackhody Radiation

The Planck function (eq. 2.36) can also be expressed in wavelength units using eq. 2.5:

lire: l
3* = A5 eke/MT _ 1' (2.50)

At high temperature or low frequency, hv/kT << I and am,”- can be approximated
by l + hv/icT. Under such conditions. the Planck function has the form
2
3” = 3;”, (2.51)
C

which is known as Rayleigh—Jeans approximation. At the other extreme of low

temperature or high frequency where hu/kT >> 1. eq. 2.36 takes the form
I! 3
B, = 2—}e‘W”. (2.52)
C

which is known as Wien '5 approximation.

 2.5 Blackbody Radiation 35

We can find the peak of the Planck function by setting BBu/av = 0. which gives

xe’
3. (2.53)
e‘—l

where x = hv/kT. The root of eq. 2.53 can be found numerically (e.g.. by Newton’s
method) to be .r = 2.8214. or

um = 5.379 x townx). (2.54)

Eq. 2.54 is known as Wien 's displacement law. A similar expression for the peak of
BA can be found by 331/3}. = 0, which gives

xe’
= . 2.55
er—I 5 ( )
where x = lac/MT. The root of eq. 2.55 is 4.965, giving the peak wavelength of

_ 0.239s
mu " T (K) cm. (2.56)

Using Wien‘s law. one can easily estimate the temperature of an object by its celor.2
if it radiates like a blackbody.
The integrated intensity of a blackbody at temperature T is

BU“) = foo BU(T)du

D
2&4?" m I3
= 7367-]; e’ _ I d1. (2.57)

The integral can be evaluated by multiplying the denominator and numerator by e“

and expanding the denominator as an infinite series:
on x} at: W
I dx = f 138—: Z 63—“ d1
0 e‘ - 1 0 null
m

=fmx32e‘Ma'x
0

on l (D

= Z: —4 f y’e-J’dy. (2.58)
n=| n 0

2. 1n astronomy, the term “color' is used to mean more than the visual colors of red. blue. green.
and so on. but is used in its extended meaning to refer to the differential intensities at different
wavelenglhs (see Chapter 3).
36 Fundamental Corrupt! ofRadiation

where y = rut. The integral in eq. 2.58 is l"(4) = 3!. where l" is the Gamma function.
We can recognize that Z: I :1; is the Riemann zeta function and eq. 2.53 can be
written as

216'?“
em = Wrongs». (2.59)

Since {(4) has a value of rr‘/90, eq. 2.59 becomes

1 211% ‘
RT =— — T
U rr(15h3c2)

= _l (2'm)

where a = 2z5k4/15h3c2 is called the Stefan—Boltzmann constant. From eq. 2.12.

the outward flux from a blackbody is a T‘.
The concept of effective temperature (Ten). commonly used in stellar astronomy,
is defined by the following equation:

F+ E on? (2.61)

We should note that effective temperature is just another expression for flu. and
contains no infomation on the spectral shape or the temperature of the radiator. For
an arbitrary astronomical object (generally not a blackbody) with a known integrated
flux F. the effective temperature of the object (Tm = (F/a)1-"‘) is the temperature of
a blackbody that would emit the same flux from its surface.

2.6 The Equation of Transfer

As light passes through a medium, its intensity changes as a result of emission as well
as absorption by the medium. In a plane-parallel atmosphere (Fig. 2.3). the intensity
is dependent only on z and 0. Consider light passing through a volume segment along
the direction 9 through solid angle do). the volume element can be approximated by
a cylinder and has a volume of dads (Fig. 2.5). If we define the emission coefficient
(jv) as the amount of energy emitted per unit time per volume per solid angle per
frequency, the amount of energy emitted in this volume is therefore j,du dtdwdads.
where s is the ray path. Using the definition of intensity in eq. 2.1 and noting the fact
that cos(9) = l in eq. 2.1, we see that the change in intensity due to emission is

d1” = juds. (2.62)

 2.6 The Equation of Transfer 37

-_____-..---_.p.
N

dz

............. d:

Figure 2.5
A schematic diagram illustrating the change in intensity as a result of emission from a volume
dads along direction dw. The amount of absorption is directly proportional to the distance ds.

Similarly. as the amount of energy absorbed is directly proportional to the light

intensity. we can define the absorption coefiiciem K._. as

(up = —Kl,[ud5. (2.63)

From eq. 2.63. we see that x” has units of cm“. xv is sometimes referred to as the
volume absorption coefiicient to distinguish it from the mass absorption coefficient.
the absorption coefficient per unit mass. having units of cm2 g" s" H: ‘. These two
quantities are related by the density of the material (p). The effect of the absorption
coefficient is to selectively remove light of a certain color from the incoming ray I...
In general. itp is a function of the intrinsic properties of the absorbing material as well
as the physical environment (temperature. density) of the material. An object whose
absorption coefficient is independent of frequency is called a grey body.
The absorption coefficient is a fundamental physical property of matter for it
defines how we visually perceive an object. Because physical objects selectively
absorb different parts of the electromagnetic spectrum. the color of the object allows
38 Fundamental Concepts ofRadiarian

us to identify the nature of the substance. The macroscopic concept of xv reflects

the microscopic (atomicfmolecular) structure of matter. and is the result of physical
processes that occur inside these structures (Chapters 4-13).
The net change in intensity after the light has passed through a volume element
as shown in Fig. 2.5 as a result of emission and absorption is

d!” = jvds - xvlvds

it = -1. + £. {2.64)
Kuds x”

The ratio of the emission and absorption coefficients is defined as the soureefitnction:

s. a ii. (2.65)
iftr

From the definitions of j, and It... we can see that 5.. has units of erg cm'1 ster‘l 55‘.
Hz", the same as specific intensity (1.).
Since Kl, is a property of the material. whereas our perception of an object isbased
on both its intrinsic preperties and the geometry and size of the object. it would be
useful to introduce a new concept integrating both quantifies that describes the efiect
of matter on light along the light path:

dry 5 —x,.(z) d:. (2.66)

r” is called the optical depth and is dimensionless. Making use of the definition of r...
we can write eq. 2.64 as

fl = I” — S... (2.67)
d1:u

This is known as the equation of transfer. The equation of transfer governs the
behavior of light when interacting with matter and is the most fundamental equation
in the study of astronomy. In a plane-parallel geometery where all physical parameters
are a function of 2 only,

dz" = x..(z) ds
ds
= 1:42); dz

= “—3) dz. (2.53)

cos 9

If r” is measured along the z axis. the equation of transfer becomes

cosflg-IE = 1M — S... (2.69)

U
 2.6 The Equation of Transfer 39

In a region of space where the radiation field is constant everywhere, eq. 2.67
implies f, = S”. If this region is in local thermodynamic equilibrium (Section 2.4),
then Kirchhofi‘s law states that a strong emitter is also a strong absorber and the ratio
of the emissivity to absorption coefficient is given by the Planck function:

Sv = 1—” = ,. (2.10)
K”

The source function is therefore given by the Planck function under local thermody-
namic equilibrium (Section 2.4). We note that 31, is a function only of temperature.
and jL and it”. both properties of matter, are related to each other also only by a func—
tion of temperature. The solution I, = B, is known as the equilibrium solution of the
equation of transfer.
We note that 1', changes in the opposite direction of 2. Consider the case of water
in a pond. The physical coordinate z measures the height of water from the bottom
of the pond1 whereas the optical depth is zero at the surface and increases in value
with depth. If we lower a light from the surface. we will see the brightness of the light
diminishes with depth. Beyond a certain depth. the light may be totally invisible. The
physical distance of this depth is dependent 0n the properties of the water in the pond
(e.g.. how dirty it is). If the water only absorbs and does not emit (5., = 0). an observer
looking directly down (0 = 0) at a light source at the bottom of the pond will find the
emergent intensity Iu(r = 0) by integrating eq. 2.67:

d1, = dry
it
1(0)
[1“(lv)]r(r) =[1fi

1.,(0) = lume‘“. (2.71)

where 1,, is the light intensity at optical depth I. Since the intensity decreases expo-
nentially with optical depth. an observer will effectively be able to see only to a few
optical depths. The utility of the concept of optical depths lies in the fact that it de-
scribes the optical properties of the medium without specifying the physical properties
(e.g.. it.) or the physical environment (e.g., z). The phenomenon that light intensity
diminishes with distance as a result of absorption and scattering can find many ap-
plications in our everyday life. Common examples include the viewing of downtown
buildings through smog, or the scattering of a light beam from a lighthouse in fog.
The concept of optical depth allows us to quantify these phenomena.
When the value of r” is small (1'u << 1). 2"” 2 l— r”, and IL(0) : 1,,(ru)(l— rv).
This condition is referred to as optically thin. When t” >> I. the medium is called
optically thick. In the extreme, optically thin can be considered to mean "transparent."
whereas optically thick can be considered as opaque. Although we perceive the air
in a room to be transparent. it does have finite absorptive power, whose cumulative
effects can be detected over a large enough distance.
40 Fundamemai Concepts of Radiation

2.7 Solutions to the Equation of Transfer

The simplicity of the equation of u-ansfer is deceptive. Although the equation has
a simple mathematical form. in practice we find that the source function is often a
function of intensity. resulting in a nonlinear equation that cannot be easily solved.
Consider the example of a dense dust cloud heated by a central star. In an optically thin
situation, an observer outside of the cloud will see starlight attenuated by absorption
by the surrounding dust. plus some self-radiation by dust as a result of the dust having
been heated by absorbed starlight. However. as we increase the amount of dust in the
cloud. there will come a time that all the starlight will be absorbed by different layers
of the surrounding dust and we will no longer be able to see the star. The emergent
radiation that is received by the observer will consist of the sum of emission from
dust near the surface as well as attenuated dust radiation from the interior. In fact. the
dust near the surface cannot see the star. and therefore is not heated by direct starlight
but by radiation emitted by other dust in its neighborhood. The emission coefficient
of the dust at each radius is dependent on its temperature. which is in turn dependent
on the local radiation field. In other words, we need the source function to calculate
the emergent intensity. but the source function is specified only after the intensity is
known at each point.
Another example is molecular-line transfer. Many of the commonly observed
molecular lines (e.g.. the rotational transitions of l2C0) are optically thick in the 18M.
This means that the photons emitted in this line will only travel a short distance before
being absorbed by another C0 molecule. This absorption (see Section 5.5) can cause
the molecule to become rotationally excited and therefore changes the population
distribution of the molecule among different rotational excited states. This. in turn,
changes the source function (eq. 5.12) and the intensity of the emitted radiation. What
this means is that we cannot calculate the emergent intensity until the source function
is known everywhere. but we cannot determine the source function until the intensity
is known everywhere. Truly a catch-2'2 situation!
However, the solution to one-half of this problem is straightforward. The expres-
sion of the emergent intensity as a function of the source function can be obtained as
follows. Defining u E c059 and multiplying both sides ofeq. 2.67 by ":1” . we have

S.
i (Ive—”l”) = — —e-W. (2.72)
dr,

Since the left-hand side of eq. 2.72 is an exact differential. it can be easily integrated.
Integrating between I] and r2. we obtain

z2 .
l..(t'..u)=lv(r1.u)e'('3"'”“+—1 f S..(r)e'""1“”dt. (2.73)
LL 1'.

Hence. the equation of transfer can be solved if we know the source function at every
optical depth. EquatiOn 2.73 also has a simple physical interpretation. The intensity
at every point in the medium is the sum of the attenuated background light (first term
 2.? Solutions to the Equation of Transfer 41

on the right-hand side) and the emitted intensity at every point attenuated over the
distance between emission and observation (second term).
In a semi-infinite atmosPhere where r; = on, the first term on the right-hand side
in eq. 2.73 is zero. At the surface (I = 0). the emergent intensity is given by

I..(0. pt) = l foo Sv(t)e "l” dt. (2.74)

r”- 0

Equation 2.73 is known as the formal solution to the equation of transfer. Since
the source function is often dependent on the local intensity. a self-consistent solution
to the equation of transfer also requires the determination of the source function as a
function of the radiation intensity. In practice. the equation of transfer is often solved
numerically by an iterative procedure (Section 2.8).
Substituting eq. 2.74 into the definition of flux. we have a formal expression for
the emergent flux:
as Jr/2
F:(rv=0)=2nL f0 s.(:)e-"“9mecosssinadsdr. (2.75)

Through a change of variable x = sec 9. eq. 2.75 becomes

00 0'0 e—ur
FTC!” = 0) = 27: f 5,,(t) [f 2 dx] dr. (2.76)
0 I I
—H
Since E..(r) = 1°" ‘1. d: is just a mathematical expression. we therefore have
a formal expression for the emergent flurt once the source function is known:
W
FIR, =0) = 211' f 3.10520) d!. (2.77)
0

In local thermodynamic equilibrium (Section 2.4). 5., = 3,.(7‘). so the emergent flux
reflects the rate of change of temperature with optical depth.
Below we consider several examples where the equation of transfer can be solved
under certain approximations.

2.7.1 Absorption Only

If the medium only absorbs the background light and does not emit. the source
function is zero and the emergent intensity at t: = 0 can be obtained from eq. 2.73:

mo. 7:) = ttr. rue—"M. (2.78)

This is illustrated in Fig. 2.6. One example is the passage of starlight through the
Earth's atmosphere. intensity attenuates approximately exponentially with optical
depth. In photometric observations (Section 3.1). the flux of starlight decreases ett-
ponentially with the thickness of the atmosphere. The attenuation is the minimum at
zenith (elevation angle of 90 degrees), which is referred to as unit air mass. At lower
42 Fundamental Concepts ofRadiation

4.;
r. + dl, (d!., < 0)

,,._..._.z+dz(dz>0)

Figure 2.6
The attenuation of intensity as a result of passing thmugh a plane-parallel slab of thickness dz.

elevation angles. the length of atmosphere that the starlight has to pass through is
longer and the attenuation is higher.

2.7.2 Constant Source Function

In the case where the source function is a constant. eq. 2.73 can be directly integrated.
For a cloud of finite thickness at a large distance where all incoming light rays are
parallel, we need to consider only the intensity at 0 = 0:

HI = D. u. =1): l(r. be" + S(l — e"). (2.79)

An example where this approximation is applicable is free—free radiation from

an ionized gas cloud (Section 6.3). Because of the thermostat effect (Section 6.5). the
gas temperature. and therefore the source function. is nearly constant. The emergent
intensity of the free—free radiation can be reasonably approximated by eq. 2.79.
For a spherical cIoud of radius R. tlte optical depth is the largest for a line through
the center of the sphere and r decreases as we move away from the center. The
 2.7 Solutions to the Equation of Transfer 43

intensity is therefore a function of the impact parameter p, defined as the minimum

distance between each parallel light ray from the center of the cloud. The observed
flux at distance D can be approximated by a summation of intensities from a series
of plane-parallel slabs. Using the inverse-square law (eq. 2.18). the observed flux is

mm=i f Iu(P)2dip-
DZ 0
(2.80)
In eq. 2.80. Mp) refers to the emergent intensity at the surface of the cloud. Please
note that we are dropping the superscript "‘ because in emission nebulae, the emergent
intensity is much larger than the incident intensity at the surface. Assuming local
thermodynamic equilibrium (S., = B”) and no background radiation, we can rewrite
eq. 2.30 as

3/2
3(0):}; f 2nn,(1-e—"9’)cos9rtzsinsda (2.31)
0

by making use of eq. 2.79 and a change of variable p = R sin 3. If both the density and
the temperature in the cloud are uniform, then r is directly proportional to geometric
length. t(0) can therefore be written simply as In, cos 9. where rm is the maximum
optical depth through the center of the cloud (6' = 0). In this case. eq. 2.81 can be
integrated to give

_ R 1 [2+
FL(D)-.2:er(b) 1 (r,,,+1)e
t3. '- l
t3']. (2.32)

In the optically thick (r,, —v 00) limit. eq. 2.82 becomes

R 2
F,(D)=(B) 1:3,. (233)

which is the expected expression for the flux of a biackbody of angular radius R/D
(see eq. 2.18).
In the optically thin case where rm is small. e‘r- can be approximated by its
Taylor expansion 1 — Tm + til/2 — gal/6. Equation 2.82 then becomes

2
mo) = (g) any (2%) . (2.34)

Since j” = xvii, and rm = 2va, eq. 2.34 can be written as

_ (4’7" 3 )
41:1”

F D = (2.85)
"( ) 4WD2
44 Fundamental Concepts of Radiation

We note that the numerator of eq. 2.35 is the total power radiated by the cloud.
Equation 2.85 is therefore equivalent to saying that every photon emitted from the
cloud escapes from the cloud and the flux detected at distance D is affected only by
geometric dilution.

2.8 Numerical Solution to the Equation of 'li'ansfer

Because of the difficulty in solving the equation of transfer. early efforts in stellar
atmospheres often adopted the approximation that the absorption coefficient (and
therefore the optical depth) is independent of frequency. This is called the grey atmo-
sphere approximatiOn. With advances in computing power. the grey approximation
has become less of a necessity and the equation of transfer is now routinely solved
numerically under different geometries by incorporating both space and frequency
domains. Once the properties of the material are known through the specificatiort
of the absorption coefficient as a function of frequency. and the density distribution
(e.g.. as a function of radial distance r in a one-dimensional case) of the material is
given, the source function S,(r) can be written as a function of local mean intensity,
1,,(r). Beginning lwith a certain assumed initial distribution of the source function. the
equation of transfer can be integrated numerically (depending on the geometry of the
system), and the intensity, 1,0}. at every point can be detem'tined. These solutions
are then substituted back into the transfer equation to calculate a new set of source
functions. This procedure is rcpeated until convergence is achieved.
The most conunonly used geometries are semi-infinite plane parallel (l -D, where
the density is a function of 2 only, Fig. 2.3). spherical “-0. where the density is a
function of r only). artisymmetric (2-D. where there is an axis of symmetry 2 with
the density independent of dc), and a 3-D case where the density is dependent on
r, 9. and d. We note that eq. 2.69 was derived under the assumption of plane-parallel
(slab) geometry. For a spherically symmetric medium. the equation of transfer can be
written as
at sine 31
6—” — ——“= ' — 1
cos 3! r 39 J” K” D
_ 2 1
i + I ‘” L = j” — xvi”. (2.86)
31’ r 3p

cos 93—13 +stnt9cos.qtfl — Mal—l" =13, —x,,l,,. (2.37)

3z 3r r 3¢

An example of an axisymmetric case is the dust radiatioa transfer problem of a

young stellar object (YSO) embedded in a circumstellar disk. Figure 2.7 shows an
example of the solution of the equation of transfer in axial symmetry. The model
images at four different wavelengths illustrate the transfer of energy from the central
star (which emits primarily visible photons) to the infrared. which is entitled by the
 2.3 Numerical Solution to the Equation ole'ansfer 45

min 2.2 t- I

12t- INI-

Figure 2.1
Model images of an uisynunetric dust cloud with a density gradient in the 6 direction at four
wavelengths when viewed along the equatorial plane. At shon wavelengths, the image is dominated
by scattered lighl in the polar lobes. At long wavelengths. the image is dominated by thermal radiation
in the equatorial plane (from Su 2030. PhD. thesis, University of Calgary).

equatorial disk. The optical depths along the polar directions are smaller, allowing
the visible photons to escape, some of which are scattered back to the observer by
circumstellar dtht.
Since the optical depth is highly dependent on 9 (r is lowest at the polar directions
and highest along the equatorial plane). the emergent spectrum is also dependent on
the viewing angle of the system. By fitting the observed spectral energy distribution
of fluxes (Fv) between the visible and the infrared by a radiation transfer model, the
46 Fundamental Concepts ofRadiation

density distribution of the dust cloud and the properties of the disk can be derived.
assuming that the stellar properties (e.g.. temperature and luminosity) and the dust
properties are known.
For a quantum system. the solution to the statistical equilibrium equation
(eq. 2.48) can be used to obtain the source function for each transition, for exam-
ple, through eq. 5.13. This can in turn be substituted into the equation of transfer to
solve the intensity (1..) as a function of the optical depth.

2.9 Scattering
Besides absorption and emission, light can also interact with matter through scat-
tering. The electric field of the incident photon separates the positive and negative
charges of the medium. causing this oscillating induced dipole to radiate (Section
5.6). After scattering. the direction of travel or even the frequency of the photon may
change. Unlike absorption, scattering leaves no permanent change to the condition of
the scattering material. While the scattering process is dependent on the property and
the density of the material. it is not sensitive to the physical conditions of the material
as in the case of absorption. The scattering process can either be elastic, where the
energy of the photon is unchanged. or inelastic. where the energy of the outgoing pho-
ton is different from the incoming one. Raman scattering is an example of inelastic
scattering (Section 5.7).
As a consequence of scattering. light can be observed from spatial locations
that do not contain self-luminous material in certain spectral ranges. as in the case
of reflection nebulae in the vicinity of stars (Section L6). Although most objects
in our everyday surroundings are self-luminous in the infrared. they are visible to
us primarily through the scattering of light from a bright. distant. small source (the
Sun). Since our eyes respond best to visible light. scattering has the most relevance
to our everyday life. Metals are particularly reflective (effective scatterers) because
the free electrons in a metal oscillate in response to the applied electric field of the
incident light. The fact that materials have different colors is the result of selective
scattering of certain colors of the incident sunlight. Consequently. we can discern
the chemical composition or physical shape of objects by their visible image. but
not their temperature. The latter, however. can be determined by infrared imaging
(Section 3.2.1). which is the result of self-emissiou.
It would therefore be useful to define a scattering coefficient 1:: separate from
the absorption coefficient K3. The sum of the two it: + K: is called the extinction
coefiicr'ent.

2.9.1 Angular Dependence

Since direction and frequency are the only two parameters that change in a scattering
process. the scattering process can be described by a phase function denoted as
Putt. 1” -) 10%. where P is the probability that a photon of incident direction
(3'. qb’) is deflected through an angle 1,0 into direction (9, 4»). into solid angle do: with
 2.9 Scattering 47

a frequency shift from v’ to between v and v + dv. The angle 1!: is related to the
incident and scattered angles by

cos q; = cos 0 cos 6' + sin 9 sin 8' eos(¢ — e’). (2.83)

P provides the angular distribution of photons after scattering and is often expressed
in a normalized form:

dai’
f P(¢r)— = . (2.39)
43

From the definition of the absorption coefficient (eq. 2.63), the amount of energy
scattered is

d5 = lynx: cos B’da'dsdw'du’ (it. (2.90)

The amount of energy scattered into new frequency v and solid angle do) is therefore

,dardw'
dEurfiv = ,rxiPWr. v'—> u)dVdvdu 1r dt. (2.91)

where 41/ = cos B'dads. The scattering emission coefficient (jg) can be defined as
the amount of energy scattered into frequency v and solid angle dcu per volume per
unit time from all incident radiation:

j: = f f rzw'. MW. v' —> v) du'dw’

4x ‘
(2.92)
If there is no shift in frequency during the scattering process. the phase function can
be written as P(t,!r)6(u’ - v), and the scattering emission coefficient becomes

1': = x: f luta’. e') PW) ii.

it
(2.93)

and the scattering source function can be written as

S: = f Mfl’, MM)“.
4n
(2.94)
For isob'opie scattering. where the probability of scattering into every angle is the
same, P = l and

S: = I met mdi
4n
= 1,. (2.95)
48 Fundamental Concepts of Radiation

In a situation where there is no absorption and the scattering is isotropic. the

equation of transfer (eq. 2.69) becomes

cos 0% = I, — J... (2.96)

Tu

Integrating over all solid angles, we obtain

illucosfldw=flvdw-4KJ”
dc,

d.”
—" = 0. ( 2.97 )
which implies that the flux is conserved through the scattering process.

2.9.2 Refraction
For a particle much larger than the wavelength of the incident light, the inc0ming
photon can undergo either reflection or refraction upon hitting the particle's surface.
The refracted light can emerge in another surface after another refraction. or be
reflected again (called internal reflection) until it finally emerges from another surface.
The combined effects of reflection and refraction are all considered part of the
scattering process. For light that gets lost inside the particle and never emerges, it
becomes part of the absorption process.
Because of the low density of the ISM. the index of refraction (Section 5.6) of the
ISM is essentially unity and light does not change in direction after passing through a
medium. Although refraction is important in the Earth's atmosphere. it is not a factor
in the ISM.

2.9.3 Multiple Scattering

Photons scattered by a single particle can be scattered again by another particle. This
is known as multiple scattering. An example of multiple scattering is white clouds
in the sky. Clouds consist of water droplets, each of which is capable of scattering
sunlight. However, because of the size of the clouds, most droplets in a cloud are
not directly exposed to sunlight. Instead. they scatter diffuse light scattered by other
droplets. The source function at each location is therefore dependent on the local
radiation field of difitrse scattered light and the solution of the equation of transfer.3
The solution to the equation of transfer for a cloud is not an easy matter and has to be
solved by a numerical procedure (Section 2.8).

3. The mathematical problem is similar to dust emission in an optically thick dust cloud (Section
10.3.2).
 2.” Summary 49

2.10 Polarization
In addition to the direction of prepagation and frequency. electromagnetic radiation
is also characterized by its state of polarization. Radiation is defined as linearly
polarized if the plane of oscillation of the electric and magnetic field vectors remains
constant during propagation. If the electric field vector moves in a circle in the
plane perpendicular to the direction of propagation. the radiation is called circularly
polarized. An unpolarized light can be considered as an equal mixture of light
polarized along two mutually orthogonal directions.
The state of polarization can be changed upon scattering by electrons, atoms.
molecules. or solid-state particles. For Thomson scattering (Section 5.7), an unpalat-
ized light acquires a degree of linear polarization given by

l — cos2 6
= —— 2.98
p l + cos2 3 ( )

after a single scattering. where 0 is the angle of scattering. We can see that the light
will be 100% polarized when the viewing angle is perpendicular to the direction of
the incident radiation.

2.11 Surru'nary
The equation of transfer is the most fundamental equation in astrophysics. By ob-
serving the emergent radiation at different frequencies (FLU = 0)), we can obtain a
spectrum. which in turn allows us to determine the physical processes responsible for
the emission. absorption. and scattering. From the spectrum. we can infer the Optical
depth and therefore the absorption coefficient, which are related to the properties of
the emitting and absorbing material. Since each ion. atom. molecule. and solid have
their unique spectroscopic signatures. we can determine the exact identity of the ma-
terial by comparing the observed spectra with laboratory data. Since the efficiency of
radiation mechanisms is often dependent on the excitation conditions. which in turn
reflect the temperature and density of the surrounding medium, we can also learn
abOut the environment under which the emissionr‘absorption taltes place.
Although most solutions to the equation of transfer are obtained in one dimension,
the increasing power of computation enables us to solve the equation of transfer in two
and three dimensions. therefore allowing us to discriminate different geometries from
the observed emergent spectrum. From the absolute strengths of the line or continuum
radiation. we can derive the amount of material present. The relative abundances
of different species provide the boundary conditious from which we construct the
formation and destruction models: nucleosynthesis for atomic elements. chemical
network for molecules (Chapter 14). and condensation conditions for solids (Chapter
13). The fact that so much quantitative information can be derived from just radiative
data is a testament to the great achievement of modem astrophysics.
50 Fundamental Concepts ofRadiation

The derivation of physical parameters from radiatiOn data requires assumptions

about the energy distribution of radiation and matter. whether the Planck, Boltzmann,
or Saha conditions apply. and how the kinetic. excitation. or radiation temperatures
are coupled. Due to the diluteness of the density and radiation field in the ISM. the
conditions of local thermodynamic equilibrium are almost never satisfied. Except
in highly explosive situations where the dynamical time scales are too short for
statistical equilibrium to be achieved. the steady-state assumption is generally valid
in the ISM. Therefore the ISM allows us to study physical and chemical processes
in nonthermodynamic equilibrium conditions and provides us with insights into
processes not present in laboratory conditions.

Further Reading

For an analytical and approximate solution to the equation of transfer. see

Chandrasekhar. S. I950. Radiative Transfer (Dover).

For detailed treatments of the problem of radiation transfer and its application to stellar
atmospheres. see
Mihalas. D. I978. Stellar Atmospheres. 2nd edition (W.H. Freeman).
Aller, L.H. 1963. The Atmospheres of the Sun and the Stars. 2nd edition (Ronald Press).

Exercises

. Show that for a blackbody, the maximum value of AFA is 0.736 times the total
flux. This is particularly convenient in a system where there are several emitting
blackbodies. for example. a binary system. a star with a circumstellar disk, and so
on. By plotting the observed total fluxes in AF,” it would be easy to determine the
relative contributions from each component to the total flux from just glancing at the
peaks of the components.
. A plane-parallel atmosphere of infinite depth has a source function of the form

5. =0 + hr... (E21)
where a and b are constants.

0 Calculate the emergent specific intensity (1:) as a function of angle (9) at the
surface (rv = 0), assuming that there is no incident radiation. Show that the
emergent intensity is characteristic of the value of the source function at about
optical depth unity along the line of sight.
- Calculate the average intensity in the upper hemisphere (If).
- Calculate the emergent flux Ff.
 Exercises 51

3. A distant uniform sphere of gas with radius r subtends an angular radius of 90 in

the sky. Assuming that the volume absorption coefficient (K) is uniform within the
volume and there is no background radiation.

(a) Calculate the optical depths along different impact parameters p as a function of
to. the maximum optical depth through the center of the sphere (p = 0).
(b) Assuming that the source function is given by S = a + In (a and b are constants)
and the sphere is located at a large distance and all rays are parallel (u. = l),
calculate the emergent intensity at each impact parameter p.
(c) Find the total flux from the sphere in terms of a, b. 90. and to.
(d) Ifa + b = 10b = 314104 K). 90 —10 3 arcsec and to is 108 at 3000 A. what is
the emergent flux in Jy?

4. A nova ejects its envelope at a constant rate of 10 3 Mg, yr 1 at a velocity of

2000 km s" 1. If this ejecta is made up of pure H and is totally ionized. calculate the
radius of the pseudo-photosphere (surface of r = 2/3) after 1 day assuming that the
opacity in the ejecta is dominated by electron scattering with a cross section of

2 2

ap-EE( e ) . (52.2)
3 in ft:2
Assuming that the nova maintains a content luminosity of 6000 La. thmughout
the outburSt, calculate the change of the effective temperature of the nova as a function
of time between: = l — IO days.
5. A strange star A is found to have a constant F; of 10“2 erg cm"2 s“' A" between
3000 and 8000 A and zero outside these wavelengths. Assuming that it has a radius
of IO' 1 cm and is located at a distance of 1 kpc. what is the effective temperature of
this star? Another star B has a constant Fu of l .ly over the same wavelength range
and has the same size and distance as star A: what is the effective temperature of this
Star? Would the two stars appear to have the same color? If n0t. which is the bluer
star?
6. A planet of radius r is in a circular orbit of radius 0 around the Sun. Assuming that
solar radiation is the only heating source and the planet radiates like a blackbody,
calculate the equilibrium temperature of the planet.
In practice. a planetary atmosphere reflects pan of the solar radiation and not all
incoming radiation is absorbed. Due to the greenhouse effect, not all of the planet's
self-radiation escapes to space. if the fraction of light reflected (called the albedo) is n
and the effective emissivity is x. derive an expression for the equilibrium temperature
of the planet.
If the planet is a slow rotator. that is. the self-rotation period is comparable to the
orbital period. what effect does this have on the equilibrium temperature?
7. Estimate accuracies of the Wien and Rayleigh-Jeans approximations of the Planck
function. Find how far from the wavelength of the peak (Arm) of the Planck function
31(7') the two approximations are. accurate to within 30%.
/.3
Measurements ofRadiation

Since all astronomical observations of celestial objects are made against a two-
dimensional sky. the measurement of radiation is basically the determination of
intensity as a function of position, color, and time. In an ideal situation of infinite
sensitivity. angular resolution, and spectral resolution. f,(x. y) can be determined at
each point in the sky at all wavelengths. In practice, since the total output of photons
from a celestial object is finite and the sensitivities of astronomical instruments are
limited. the measurements of Iu(x, y) have to be binned over finite angles andfor
wavelength ranges in order for detection to be made. In other words, high spatial or
spectral resolution can be achieved only at the expense of sensitivity.
For objects of very small angular sizes (e.g.. stars). the measurement of intensity
is impractical. For example, a star like the Sun located at a distance of 100 pc will have
an angular diameter of ~ [0“ arcsec. Although the intensity of certain nearby bright
stars can now be measured with modern techniques such as spectrointerferometry, for
the majority of stars, flux is the only quantity that can be measured. By integrating
starlight over a finite wavelength range, the fluxes of stars at several colors (fM fudv)
can be easily measured. This practico is known as photometry. For example. the US.
Naval Observatory has measured the fluxes of almost one billion stars in two colors
through the digitization of the Palomar Observatory Sky Survey (POSS) photographic
plates. ln extragalactic astronomy where distant galaxies and quasars have small
angular sizes. photometry is also a widely used technique.
For extended objects (e.g., nebulae and galaxies). their brightness distribution at
a certain color can be obtained through the techique of imaging with devices such as
photographic plates. CCD cameras, or interferometers.
While the measurement of flux provides information on how much light is
emitted by an object and the measurement of intensity shows how light is distributed
across the surface of the object. it is the measurement of color that contains the
most information on the physical processes involved. In the first approximation. the
color of objects can be determined through photometric measurements over several
filters. and the resulting plot of Fv versus v is known as spectral energy distribution
(350). For faint or distant objects. the SED provides basic information on what
physical constituents are present, and through what physical processes the light is
emitted. For example. an excess of flux in the infrared and X-ray may indicate the
presence of dust and hot gas, respectively. However, the detection and identification of

53
54 Measurements ofRndt'atic-n

quantum processes. which emit light over a very Small frequency range, requires high
spectral resolution using the technique known as spectroscopy. Modern spectroscopic
observations have revealed the electronic transition of atoms (through optical and
UV Spectrosc0py). rotation of molecules (through millimeter-wave spectroscopy),
the stretching and bending of molecules (through infrared spectroscopy). and nuclear
transitions (through X-ray and garnma ray spectroscopy). Because light emitted by
moving objects is subjected to Doppler shifts. spectroscopy is also useful in providing
kinematic information. Kinematic information is important in several ways. as in the
determination of the internal expansion or rotation of interstellar clouds and galaxies,
and in the receding of galaxies through the expansion of the Universe.

3.1 Flux Measurements

Flux is usually measured by the use of a photometer. Light is collected through a

finite aperture at the telescope with a filter having a center frequency (wavelength) uo
(A0) and a filter response profile (bu (elk). Photometry is now commonly practiced at
all wavelengths from X-ray to radio. Since the ability of instruments to detect energy
flow is limited. phOIOmeu-ic sensitivity can be improved by increasing the filter width
Al. Of course by increasing AA too much. one loses the color information.

3.1.1 The Magnitude System

The brightness of objects we encounter during our everyday life varies greatly from
day to night. For example. the Sun is about 10'3 times brighter than the faintest star vis-
ible to the human eye. In order to accommodate and take advantage of this huge range
of brightness in our surroundings. our eyes have developed a logarithmic response to
brightness. so that the amount of information produced would not overwhelm the
brain. Early human Comparison of brightness of stars. such as those performed by
Hipparchus, reflects the ratios. not differences. of their relative fluxes. In the 19th
century, the concept of stellar magnitudes was formalized as a logarithmic measure
of the flux. where a factor of 100 in flux is defined as a difference of 5 magnitudes:

ln eq. 3.l. mf is the stellar magnitude observed at a specific filter f. FI =

f thbvdv is the total flux collecred over that filter profile ¢l., and FIn is the flux
over the same filter at the reference (zero) magnitude (mo).
Consequently. the definition of a magnitude is dependent on the filter response
of a particular filter system. For example, one commonly used magnitude system for
visible astronomy is the Johnson U. B. V. R. I system. with each letter corresponding
to a specific wavelength center A.) and filter profile «p, (Table 3.l). Because of the
negative sign in eq. 3.1. a star of higher flux (brighter) has a smaller magnitude.
Tire observed magnitude of a star (m f) is also referred to as the apparent mag-
nitude. In order to compare the intrinsic brightness of stars at different distances. the
concept of absolute magnitude (Mf) is introduced as the magnitude a star would have
 3.! Flier Measurements 55

Table 3.!
Central wavelengths and zero-magnitude fluxes at different photometric bands

U B V R l .l' H K L M N Q 2

10mm) 0.36 0.4-4 0.55 0.71 0.97 1.25 1.68 2.25 3.5 4.8 10.3 20 25
FmUy) 1323 4130 3731 2941 2635 1510 1016 641 232 154 36 10 6.5

Source. Hanna er al. 1934. Astr. J.. B9. 162. and Astrophysical Quantities. 4th edition. Table 15.6.

at a distance of 10 pc. From the inverse-square law and the definition of the magnitude
(eq. 3.1). the apparent and absolute magnitudes are related by

mI=Mf+Slogd—5. (3.2)

where d is the distance in units of pc.

The difference in magnitudes between two AD (e.g.. B — V) is called the color
index. Early photometry of bright stars has shown that main sequence AOV stars have
the same magnitudes in U, B. and V, so these stars are assumed to have no color
index between all bands. For bands outside of the visible, or Ly-r (Vega), an AOV
star. is defined to have zero magnitude at all wavelengths. The magnitude system is
calibrated by obtaining an absolute measurement of Fm for Vega. However. it is now
known that Vega has significant excess in the far infrared. and is not appropriate to be
used as the zero standard for all colors. For this reason, the use of the magnitude
system is generally limited to the visible, near, and mid-infrared. For example.
although the measurements of radio fluxes from unresolved objects (stars. quasars)
are routinely perfouncd. the magnitude system is never used in radio astronomy. As
multiwavelength observations are becoming more common. it is more convenient to
use flux rather than magnitudes as the unit of measurement to compare the brightness
of an object at different wavelengths.
If a photometric measurement is made with a broad filler. then the total flux
measured (F : f F,¢..dv) can be related to the monochromatic flux (Fm) at the
central frequency (we) only if the exact spectral shape of the source is known. For
example, the IRAS satellite made an all-sky survey in four (12. 25. 60. and 100 pm)
bands. and the fluxes of point sources are catalogued in the IRAS Point Source
Catalogue (PSC) as monochromatic fluxes in units of Janskys (Iy. Section 2.2). With
no a priori knowledge of the spectral shape of the sources, a flux distribution of
fr or v“ is assumed in the PSC. 1f the actual spectral shape of the source is different.
then a color correction has to be applied. Since

1": F,“ [(Fv/Fm)¢udu

= “0(PSC) [tn/mam. (3.3)

56 Measurements ofRadiation

I I I I I I I I I I I I I —I I I I

12-pin band 25—pm band 60-pin band too-pm band

Relative system spectral response

1.0 -

0.3 -

0.6 -

l l I I I I l J l l I L l I l l l

7 3 10 I2 IS 20 10 40 60 30 [00 120140
Wavelength (p m)

Figure 3.1
Profiles ofthe four photometric filters of IRAS.

we can define a color correction factor K = Fl.“(PSC)/F,o. where K can be shown

from eq. 3.3 to be

_ f(F../F.,o)¢,,du
_ . 3.4
f(fu/fu0)¢udv ( )

Since the IRAS filters are broad (Fig. 3. I). the color correction factors can be quite
large. For example. a star with the spectral shape of a 10.060-K blackbod}l will need to
have color correcrion factors of 1.45. 1.4 l. 1.32, and l.09 applied to the IRAS PSC 12-,
25-. 60-, and loo-um fluxes, respectively. In these days of multiwavelength observa-
tions. it is common to combine photometric measurements from different instruments
into a single Fv versus 1: plot (SED). Since different photometric measurements have
different filter profiles. it is necessary to perform the proper color corrections before
translating lhe observed fluxes (F) into monochromatic fluxes (Fu).
Although photometry is most commonly used to determine the shape of the emis-
sion spectrum of continuum processes, the finite widths of the filters mean that the
measured fluxes can be conlantinated by fluxes from emission or absorption lines.
or due to sudden changes in the continuum (e.g.. the Balmer jump in bound-free
absorption, Section 4.3). Since molecular emission lines are strong in the submm re-
gion (Chapter 7). photometric measurements in the submm designed to measure dust
continuum emissions (Chapter 10) often include contributions from line emissions.
Considerable care must therefore be exercised in the design of filters (in the choice of
A0 and AA) to avoid known strong lines or features. In the infrared. filter designs have
 3. I Fher Measuremenrs 57

I l l I I l fir I l I I l I q

50 - . ‘
. IRAC total Instrument throughput -

40 ._ _

E.. 30 _Z _
2
E»an -- .
:l
a
e - 2
IE 20 - _

10 ..‘- 3.
E E
1
-.
. ~o w} .
_ n v- -
"l . ll . '
0 4 10
Wavelength (p m)

Figure 3.2
Total tl'u'oughput of the four photometric filters of the Infrared Army Camera of the Spirzcr
Space Telescope. The throughput includes transmission of the telescope. optics. and quantum
efficiency of the detectors (from Fazio er at. 2004. AN3, [54. IO).

also taken into consideration the atmospheric transmission and are placed optimally
in atmosphere windows where the transmission is the highest.
Broadband filters can also be placed to incorporate major emission lines or
features. For example, the 3.6-. 5.8-. and [LO-pm filters of the Infrared Array Camera
(IRAC) of the Spitzer Space Telescope (Fig. 3.2) cover the 3.3-. 6.2-. and 7.7-um
aromatic infrared bands (Section l2.l). whereas the 4.5-um filter covers the 4.052-
um recombination line of H (Bracken (I. n = 5 — 4. Section 5.1 1.3) and the 4.695-um
rotational line of H2 (Section 7.7.1). Imaging using these filters can therefore map
out the distribution of aromatic grains and hydrogen molecules in the Milky Way and
external galaxies (Section 17.3).
From eq. 3.]. we have the following expression for the color index:

m1 — m2 = 2.5103(F2/F.) + C12. (3.5)

Where C” = 2.5 Icahn/1’20) represents the difference in magninide between the

zero points of the two filters. For objects whose fluxes can be approximated by
blackbodies. their color indices can be calculated using eq. 3.5. A plot of two different
58 Measurements ofRadiation

2.5
U—B (magnitudes)
0
Ln

l - l 1 | I | .

0.0 0.5 1.0 1.5 2.0

B— V (magnitudes)

Figure 3.3
Color—color diagram of 7195 stars in the Bright Star Catalogue with UBV magnitudes. The B — V
color indices range from -- —0.3 (contsponding to T ~ 30.000 K) to ~ 2 (corresponding to T w
2000 K).

color indices is known as a color-color diagram. Figure 3.3 shows that the visual
colors of normal stars fall on a well-defined sequence. which traces the temperature
of the star.
The IRAS PSC fluxes can also be expressed in a magnitude system provided that
the zero-magnitude fluxes in these bands can be obtained by using late-type stars
with no infrared excess as calibrators. Beginning with the zero-magnitude fluxes of
28.3. 6.73. 1.19. and 0.43 Jy at 12. 25. 60. and 100 um. respectively. and applying
the color correction factors for normal stars. one finds that the zero—magnitude fluxes
for the IRAS bands become 40.469. 9.422. [.565. and 0.469 Jy. respectively. The
corresponding color indices for the IRAS filters are

[12] — [25] = l.582 + 2.5 logm[Fl.(25 ,um)/Fv(12 urn)] (3.6)

[25] — [60] = [.945 + 2.510gm[F,,(60 um)/Fv(25 um]. (3.7)

 3.] Flu: Measuremeru: S9

103.0(1505 ymylfitllrum»
.12 .m —o.s —o.s —o.4 —o.2 0.0 0.2 0.4
5.0 | I I f - l I l I 1 I |_ w 0-3

4.0 - ' Me _ - 0.4

. . (0H)E . . q

log.a(l&(60um)/Mi(25flm))
- (omit
3.0 l—
[251 - [60]

2.0 —

0.0 F

—l.0 —

-2.0
-0.5
[121-425]
Figure 3.4
(MS color-color diagram of I I6] M stars (filled circles), 33'! Ol-UIR stars with the silicate feature in
emission (triangles). and 135 OHIIR stars with the silicate feature in absorption (squares). Also plotted
as a dotted line is a blackbody curve with temperature marked (from Kwolt. Volk. and Bidelman.
I997, ApJS. "2. 557).

Figure 3.4 shows an IRAS color—color diagram of O—rich evolved stars. The stars lie on
a sequence that is defined by the color temperature of the circumstellar dust envelope.

3.1.2 Aperture Response and the Telescope Beam

For stars where the angular sizes are usually small. the size of the aperture is not an
issue. However. for a star with an extended atmosphere or a circumsteliar envelope.
or for an extended object like a nebula or a galaxy. the flux collected at the telescope is
dependent upon the aperture used. While the aperture response for an optical telescope
can be considered to be uniform. it is not the case for radio telescopes. in general. the
telescope beam has a form P(6. dr) and the flux over the area of the beam is

Fl. = ff 1.,(9. ¢)P(B, oi) sin 9d9d¢. (3.8)

60 Measurements ofRadiation

If the size of the source is much smaller than the beam. then the flux measured will be
very close to the actual flux of the source. In the extreme case. as in the observation
of a star. the source is referred to as unresolved. If we define the average intensity of
the source as

F .
I‘ = ___v— (39)
” H P(9.¢)sin9d6d¢'
then iv is much smaller than the actual intensity (10(9. 45)) of the source. [.11 the case
that the source is much larger than the beam. then the flux collected by the telescope is
smaller than the actual flux. and the average brightness approaches the true maximum
intensity of the source 1-, —> tum, (b).
1n radio astronomy, intensity is often expressed in units of temperature. The
brightness temperature (Tb) is defined as the temperature required for a blackbody to
emit the same intensity at the same frequency as the source:

1” a sum). (3.10)

At low frequencies where the Rayleigh—Jeans law applies. the brightness temperature
is directly proportional to intensity:

C2
b: mt... (3.11)

Another commonly used concept is the radiation temperature. which is defined as

62
T a —I.,. 3.12
" zuzt ( )
Combining eqs. 3.10 and 3.12, we have

TR: “1 ’13. (3.13)

a"; — l k

We can see that TR = Tb only at low frequencies.

When intensity is expressed in brightness temperature. the equivalent of the
average intensity I, is called the antenna temperature:

__ f f TAB. ¢)P(0. e) sin 9d0d¢ (3.14)

TA _ f f PIEB. to) sin 0d9d¢
We should note that while Tb. TR. and TA have units of temperature. they have the
physical meaning of intensity and are frequency dependent.
 3.2 Measurement of Intensiry 61

As a simple example. consider a uniform brightness source of angular radius

a observed by a telescope of uniform circular aperture with angular radius B; then
eq. 3.l4 gives TA = Tb when the some fills the beam. If a < B. then the antenna
temperature is given by
2
TA = (g) r... (3.15)

This effect is called "beam dilution."

3.2 Measurement of Intensity

3.2.1 Direct Imaging
The measurement of intensity or brightness distribution is limited by a combination
of telescope aperture. instrument resolution. and the atmosphere. For many decades.
astronomical imaging in the visible relied on the use of photographic plates. The
principle of photography is based on the interactions of photons. collected through
an optical device such as a camera. telescope. or spectrograph. with the silver halides
(BrAg) that form the basis of the photographic emulsion. The emulsion support may
be a glass plate or film. Incoming photons provoke random chemical reactions on the
emulsion grains. with the typical grain size varying between 25 and 75 Iurn. Smaller
grain sizes result in higher resolution and require a longer exposure time. The pho-
tographic density of emulsion responds in a logarithmic manner with light intensity.
which is appropriate for astronomy since star brightness is scaled in magnitudes to
fit the human eye visual response. The main drawback of the use of photographic
plates is that photographic emulsions suffer from nonlinear msponsc to intensity as
well as low efficiencies in the red. in particular longward of 5000 A. The traditional
advantage of photographic plates is their large area, but with increasingly large format
CCDs being available. this advantage is rapidly disminishing.
The development of solid-state detectors based on the principle of the photo-
electric efl'ecl has revolutionized astronomical imaging. The charged-couple device
(CCD) employs photosensitive picture elements (“pixels") packed closely spaced
together in the form of a two-dimensional array. Upon incident radiation. an electron-
hole pair is created. Through a potential well created by electrodes. the electrons are
accumulated in this well over a specified integration period. At the end of this period,
the CCD stores a two-dimensional charge distribution in proportion to the number
of photons absorbed by each pixel. The charges are transferred row by row by ap-
plying a pulsed variation of the potential toward the output register. Consequently.
so long as the accumulation of charges is not saturated (the We" is not full). CCDs
are characterized by a linear response to light. Very high angular resolution images
can be achieved through the reduction of pixel sizes. Because of the linearity of the
signal. absolute calibrations are easy to obtain. resulting in good-quality photometry.
By combining exposures with carefully chosen integration times. images of dynamic
range as high as 100.000 are possible.
62 Measurement: of Radiation

In the near infrared. photoconductors. based on the principle of photons exciting

an electron into the conduction band. are used as detectors. Photovoltaic arrays
of indium antimonide can operate in the wavelength range of 2.3 to 5 am. The
compound mercury cadmium telluride (HgqudITe) can be used to produce Very
sensitive detectors where the composition fraction I can be adjusted to extend the
cutoff wavelength. For example. the Near Infrared Camera (NIRCam) of the James
Webb Space Telescope has a 4096 x 4096 HgosstOASTC array for 0.6— to 2.311.111
imaging. and another 2043 x 2043 Hgo_mCdo_3oTe array for 2.4- to S-trm imaging.
At longer wavelengths. impurity-band conduction (lBC) devices can be used from
5 to 28 Itrrn. For example, the Infrared Array Camera of the Spitzer Space Telescope
consists of four 256 x 256 arrays. The two arrays at 3.6 and 4.5 um are based on InSb
detectors. whereas the two arrays at 5.3 and 3 am are based on SizAs detectors.
Germanium photoconductors doped with gallium or antimony can detect infrared
radiation between 50 and [00 am. For example. the Multiband Imaging Phorometer
(MIPS) of the Spirzer Space Telescope has a 32 x 32 Ge:Ga array for imaging
at 70 am. When a stress is applied to the germanium. the cutoff wavelegnth can
be extended to 200 am. Examples include the Photodetector Array Camera and
Spectrometer (PACS) for the Herschel Space Observatory. which has two 16 x 25
GezGa detector arrays for 57- to 210-,um spectroscopy.
In the far infrared between 100 and tom ,um. bolorneters. based on the principle
of varying resistivity in response to changing temperature induced by the absorption
of a photon. are the most common detectors. A bolometn'c detector consists of a metal
film to absorb radiation and a doped Si or Ge thermometer to measure the temperature.
For example. the Spectral and Photometric Imaging Receiver (SPIKE) of the Herschel
Space Observatory comprises arrays of 43. 33. and 139 elements for imaging at 250.
360, and 520 am. respectively.
The heterodyne technique is commonly used in radio astronomy. Heterodyne
mixers mix the incoming signal with a local oscillator to produce a beat frequency
that is easier to amplify. At infrared wavelengths. photonic mixers are now under
development. Superconductor—implater—superconductor (SIS) tunnel junctions are
now commonly used as heterodyne down converters at waveleng1hs longward of
300 pm.

3.2.2 Interferometry
The resolution of a telescope is limited by its diffraction pattern. For a circular aperture
of radius R. the diffraction pattern is

2 Zitli‘sinfl 1
t=to[i(— 7“] .
2rd? sin 9
(3.16)
it

where J] is the Bessel function of the first kind and 10 is the peak intensity at 6 = 0.
 3.2 Measurement oflntensit'y 63

The angular resolution of the telescope can be approximated by the first zero of
the diffraction pattern. which is given by

6 ~ 3.83%
_ ZnR
..._.—.
1.22.1 3.7
2R (I)
commonly known as the Rayleigh criterion. While a l-rn diameter telescope has a
diffraction limit of 0. t3 arcsec at 0.5 am, a radio telescope Operating at A 6 cm will
need to have a diatneter of [20 km to achieve the same resolution. Since weight
and surface deformation become increasingly problematic with increasing apeI1ure
size. there is clearly an upper limit to the size of a single-dish telescope. As of 2005.
the largest steerable single-dish telescopes are the lOO-m Green Bank Telescope of
the National Radio Astronomy Observatory in Green Bank. West Virginia. and the
IOU-m Efi‘elsberg Telescope of the Max Planck Institute for Radio Astronomy in
Bonn. Germany. Since the demand for surface accuracy increases with increasing
frequency. millimeter or submillimeter-wave telescopes are necessarily confined to
smaller apertures. Among the largest single-dish millimeter telescopes are the 45-m
telescope in the Nobeyama Radio Observatory in Japan and the 30—m telescope of
the Institut de Radioastronomie Millimétrique (IRAM) on Pico Veleta in Spain. For
submillimeter telescopes. the largest is the lS-m James Clerk Manvell Telescope on
Mauna Kea. Hawaii, followed by a number of lO-m—class telescopes. including the
IO-m Caltech Srrbrrrr'llr‘nreter Telescope on Mauna Kea. Hawaii. the lO-m Henriclr
Hertz Telescope on Mt. Graham. Arizona. the Max Planck 12-m Atacama Pathfinder
Experiment (APEX) in Llano de Chajnantor. Chile. the Japanese lO-m Atacama
Submillr'meter Telescope Experiment (.4575) in Pampa la Bola. Chile. and the lO-m
South Pole Submr'llr'meter Telescope at the South Pole.
An alternative way to achieve higher angular resolution without increasing the
aperture is through the use of interferometers. By placing antennas kilometers apart.
signals from distant celestial sources (which have essentially parallel rays) will arrive
at each antenna at slightly different times, and by comparing the phase difierences
between antennas, very small changes in the signal origin can be discerned. By con-
structing an array of telescopes with different separations, images can be constructed
from the phases and amplitudes measured at each antenna. This technique. known as
aperture synthesis. has become the most common technique for imaging in the radio
wavelengths. and is rapidly being expanded into shorter wavelengths such as the in-
frared and visible. An example of such expansion into the near infrared is the Very
Large Telescope Interferometer on the mountain Paranal in Chile. consisting of four
large S-m telescopes and a number of smaller auxiliary telescopes.
At the centimeter wavelengths. the most powerful radio interferometer array is
the Very Large Army in New Mexico. which consists of twenty-seven 25-m dishes.
At mm and submm wavelengths. there are the Plateau de Bare Interferometer Array
(6 it IS m) in France. the CombinedArrayforResearch in Mtllr'rrreter-waveAstronomy
(9 x 6 rn + 6 x 10 m] in California. and the Snbmt'llr'meterArray (B x 6 m) on Mauna
64 Measurements ofRadiation

Figure 3.5
A schematic diagram illustrating the phase delay of a two-element interferometer.

Kea. A 64-element Atacama Large Millimeter Army (ALMA) is under construction

in Llano de Chajnantor. Chile.
Let us consider a two-element interferometer where two antennas. each with a
beam pattern of PH (9). are separated by adistance of L (Fig. 3.5). The phase difference
between light from a distant point source arriving at the two antennas is 2n L sinfl/A
radians. If we choose the reference point of zero phase as the midpoint between the
two antennas, then
E = isle-W? + EzeW’. (3.13)
where 11'! = 21rL sin 9/). and E. and E; are the electric fields of the radiation at the
two elements. If El = £2 = £0,

E = 2.50 (M) (3.19)

= 250 cos (g) . (3.20)

If we define the power P as IE 12. then

10(9) = 415012 cos: (g) . (3.21)

Defining 31(9) or lEfllz as the normalized power pattern of each individual telescope
element. We have
 3.2 Measurement ofIntensity 65

P0?) = IP,.(9)I(I +¢06tlt). (3.22)

and the function (I + cos 11;), called the array pattern, is the result of interference of
radiation from each element. The power pattern is zero when it; = (%J sin 9 = n.
or 0 = arcsin(1/2L). For small angles, 9 : )t/2L. These zero points are referred to
as fringes.
The separation between successive fringes (or fringe spacings) is 29 = (1/1.).
This quantity defines the resolving power of the interferometer. Instead of 1/ D (where
D is the size of the minor) as in the case of a single-dish telescope, the angle 9 is
inversely proportional to the separation between the elements. Since the only practical
limit to L for an Earth-based telescope is the size of the Earth. extremely high
resolving power can be achieved by the technique of interferometry. For example.
at the wavelength of 2cm. 3. two-element interferometry with spacing of 5 km can
achieve an angular resolution of better than 1 arcsec. In comparison, the largest single-
dish radio telescope with a diameter of 100 m has a resolving power of 41 arcsec at
)t = 2 cm.
Maxima of the array pattern occur at it! = 2nn, or

em = sin-1 (2:171) , (3.23)

where n is called the fringe order.
Let us consider a one-dimensional source of surface brightness distribution I (9)
and angular sin a at an angle 30 observed by a two-element interferometer. If a is
small compared to the beam pattern of each individual element, Pam) is approx-
imately constant across the source and the array pattern dominates the change of
response with 9. Substituting eq. 3.22 into eq. 3.3. we have the flux observed by the
interferometer:

HBO) = 31(0)
"/2 2n L
[(9) [1+ cos [T sin(t90 — 6):” d9. (3.24)
-a/2

Assuming that the source is continuously tracked by each of the away elements (as is
the case at the VLA) such that Pflw) : l, we obtain
all til/2 an
Fmo) =1 f(9)d9 +f [(9) COS [T sin(90 — 3)] d0. (3.25)
—a/2 —a/2

The first term is the flux (F0) of the source. For a small source, 00 — 9 << I: and
sin(90 — 9) ~ 60 — 6. and eq. 3.25 can be Written as

0/2
Fwo) = F0 + [cos $90] I [(9) cos [#6] d6
—a/2

a/2
+ [sin flso] f 1(9) sin [M—Le] d9, (3.26)
A "0/2 A

afterWe makeuse ofthe trigonometric identity cos(00 - 6) = cos 90 cos 3 + sin 90 sin 9.
66 Measurements of Radiation

Equation 3.26 can be expressed in the form

F090) = Full + V(9o- Sill. (3.27)

where S; = MA is the array spacing in units of wavelengths, and

V(00. 3;.) = Fl cos(ZrtSA00) 1(0) cos(2n516) d6

0

+ Fl sin(21r5190) r09) salon sic) d9. (3.23)

0

It is possible to separate W60, 3*) into two components: an amplitude V003”

term and a cosine term. If we express the pointing angle of the interferometer 6 as
60 —- A9, where 60 is the center of the extended source, we can write

HS“. 3;) = 110(5)) cos[2n.§'y(60 — 119)]

= Vo(31)[cos(2:r3160) c0301! $1136)
+ sin(21'r 3190) sin(23'r SAAB) ]. (3.29)
Comparing eq. 3.29 with eq. 3.23, we have

Vo(SA)cos(21rSAA9)=—;—fi(9)cos(21r316)d6 (3.30)
0

V061) Sin(21rSAA9)= 11—] i(9)sin(2n316)d9. (3.31)

o
Multiplying eq. 3.3] by i and adding to eq. 3.30, we can express the result in
complex variable notation:

. ‘1"2 .

VMSQe’hSiM = FL I [(0)31235md9. (3.32)

0 a,-‘2

This equation is called the complex visibiiiry function, and the function V061) is
refen-ed to as the visibility function.
As the Earth rotates. both 90 and 0 will change as the interferometer tracks the
source. An electromc delay can be added to the signal path from one antenna so
that there are no fringes at 60. At position A0 from the center. fringe patterns will be
different. For this reason, A6 is sometimes referred to as thefringe displacement from
the position of a point source. By measuring the amplitudes and phases of the fringe
patterns. we can observationally determine the visibility function. In eq. 3.32. V061)
and 2‘2" 5* ‘59 represent the amplitude and phase. respectively. of the fringe pattern.
For a small source. 1(0) is zero at large angles and the limits of the preceding
integral can be extended to infinity with minimal errors. In this case, we have
00

v°(51)e"1"5139=Fi f [(9)6izfl'fisd9. (3.33)

D in:
 3.2 Measurement ofl'nlenst'ry 67

We can see that Va is the Fourier transform of the surface brightness distribution, and
therefore I (9) can be obtained by the inverse Fourier transform:
on

m9) = F0 f vasor’mfle-M’dsl. (3.34)

—00

By measuring the visibility function V0051) at different baselines L, it is possible to

reconstruct the intensity distribution of the source. This technique is called aperture
synthesis.
For a symmetric source where I (6) = l (—9). the only nonzero part of eq. 3.32
is eq. 3.30:
all
V001) cos(2n 51.59) = :i:Fi 1(9) cos(27r SLG) d0. (3.35)
0 —°f2

From eq. 3.23. we can see that the visibility function of a symmetric source has the
same form (a cosine function with maxima occurring at the same 6) as a point source,
and therefore has no fringe displacement (A9 = 0):

a/2
tram) = ii I (a) mean ska) d9. (3.36)
F0 —a/2

In Figure 3.6. we show the visibility functions for a symmetric source of a fixed size.
and a nonsymmetric source where I varies linearly with 9. We can see that A6 is
nonzero for a nonsymmetric source.
For a source of size a and uniform brightness 1(9) = Fo/a, eq. 3.36 becomes

Sin[21rS,\(g-)]
V S =:i: (3.37)
°( *) zzsng)
A plot of eq. 3.37 is shown in Figure 3.7. We can see that at zero baseline (8; = 0).
V0 =1. and V0 = 0 when 2N31(%) = PUT. or
9 I 3

5A = (3.33)
Besides at S; = 0. local maxima (positive or negative) of the visibility function occur
at 21rSy(a/2) = t¥lm or
_ (211+ l)
S,‘ 2“ (3.39)

From eq. 3.31 we can see that for an unresolved source where the source size
is much smaller titan the fringe spacing (31;). VO(SL) : I. For an extended source
that is totally resolved by the telescope beam (0 >> 33:), V061) —> 0.1herefore. a flat
visibility curve implies an unresolved source. and a rapidly declining visibility curve
implies a highly resolved extended source.
68 Measurements offladiarian

-l.0 “'

Figure 3.6
The visibility as a function of 00 for symmetric source (uniform brightnem l = in over finite
width a centered ate = 0. shown as the dark line) and nonsyrnmctric source (! = h(l/2 + Ola).
shown as the light line) as calculated from eq. 3.28.

Similarly, a visibility function can be constructed for lhe two-dimensional casc.

(I) U) _
V(u, v) =f f [(1. y)e‘1"("+”’) dx dy. (3.40)
—oo -CD

where S; = «in! + vi. Eq. 3.40 can be transformed to polar coordinates (r. 9) by
writingx=rcosfl.y=rsin0ind1eslcyplaneandu = S; cosqb. u=51sin¢inthe
u — 1: plane.
For a circular symmetric source centered at x = 0, y = 0, I (r. 9) = I (r) and
eq. 3.40 becomes

2
”3140:!0 n[onr1(r)e"?-"'Sxtm¢m0+un¢sinayd, d9
o
co 2:
=f rl(r)f ei'ZJrrS‘ “(a—”Jr d9
0 u
an In
=f ”(Hf cosIZrIrrS,L cos(6 — ¢)]dr d9
0 0
CD 27:
+if run] sin[27rr$,L cos(9 — ¢)] dr d0. (3.41)
0 0
 3.2 Measurementoflmensiov 69

Figure 3.7
The visibility curve for a symmetric uniform brightness source.

where the imaginary term can be seen to be zero because the sine function is odd
and its argument is symmetric w.r.t. zero. The real part of eq. 3.41 is independent of
4!: because its argument 27175} cos(9 — W covers the same range of values over the
integration regardless of its initial value. The inwgral over 9 can be identified as the
integral expression of the zeroth-order Bessel function Jo:

2n
10(u)=i f e'"°°“du.
211' o
(3.42)
where u = 21: 311' and u = 0 — d. The visibility function (eq. 3.4 l, a function only of
5;) can therefore be written as

W310“! 2nrl(r)Jo(21rr51) dr. (3.43)

0

As in eq. 3.34, the intensity can be expressed as a function of visibility:

CD

I (r) = 211' f S; V(SA)JO(21rrSA) (15*. (3.44)

O

For radio sources that are only marginally resolved. their structures are often
difficult to determine from intensity maps. In some cases. the visibility curve analysis
can be very useful. For a circular symmetric source, all the fluxes are in the real
part of the visibility function. and the real component of the data can be averaged
10 Measurements quadialion

50 I I l I l

40 '4. Me 2-2 _
”Us“

1%
30 — x}. '-

‘El ‘1.
: 20 -
3
‘4 ¢;.'
-
E ‘1‘...

to — ‘1".“‘1"!-
-
\‘\ '1 ----- if

0 ‘ “~._ _____
'1‘ l-FT 3":1’,
I I .. ‘i -- i’T

4° 1 I l I I
0 [00 2C!) 300 400 500 6C0
Baseline. b (ll)J 1)

Figure 3.3
Model fittings to the visibility curve of Me 2-2. The uniform sphere and core—halo models are
shown in dashed and dotted cin'ves. respectively. For the core-halo model. the fluxes and the
diameters of the core and the halo components are 24 and 15 nin. and 0.94 and 1.64 mete,
respectively.

over angle and binned over projected baseline to improve the signal-to—noise ratio.
Figure 3.8 shows a plot of the visibility amplitudes of Me 2-2 as observed by the WA.
By comparing these plots with model visibility curves. the structure of the source can
often be derived.

3.2.3 Multi-element Array

The ease of the two-element interferometer can easily be generalized to a multi-
element array. For a linear array of n equally spaced elements,

E=Eo(1+e"* +3” + - --+e"‘"'”*). (3.45)

where g: = ¥ sin a. Multiplying eq. 3.45 by e” and subtracting the product from
the original, we have

E(I — l"")=Eo(l —e""*) (3.46)

egg—""22 -gL.!t)
E = 50 (3.41)
age—£5! —e£!') .
 3.2 Measurement aflnlensil‘y 71

Grating lobe H

5(0)’

WWW,
i
:15;

Figure 3.9
The any pattern for a l0—elemem away.

We can choose the center of the array as the reference point by multiplying
eq. 3.47 by e "“1"". In this case. eq. 3.41 becomes
elat—e'i'nit
E=Eo (—e!¥_e_‘*)

= r sum?) . (3.4s)
° snug)
The array pattern for an array of n = 10 elements is shown in Figure 3.9.
At small 0. sins :0 and rl1ezerosofeq.3.4-B occurat

(5) 23519 =mn’

2

in l
n 3*
0: —-—. (3.49l
The beam width of the array can be defined as the interval between first nulls.
or 21:13,“ The angular resolution of the array is therefore directly proportional to lhe
72 Measurements of Radiation

number of elements. Outside of the main beam, secondary maxima occur at

E'- = mrr
2
m
6 — 5“. (3.50)

where m is an integer. These maxima are referred to as grating lobes. For a IO—elernem
array with l-ltm baseline operating at a wavelength of J. = 2 cm. the beam width is
0.8 arcsec and the position of the first grating lobe is located at 4 arcsec.
Since these grating lobes can also pick up the radiation from the source. it would
be desirable to suppress them as much as possible. One possibility is to make use of
the diffraction pattern of the individual dishes. The first minimum of the diffraction
pattern of a single dish of diameter D is 0 = 1.221; D. By equating the positions of
these minima with the maxima of the array pattern. we have

iD z i.
5'.
(3.51)
3.2.4 Aperture Synthesis
From Section 3.2.2 we see that one can obtain the brightness distribution of an object
by having a complete sample of the (u. 0) plane. For a linear array. the rotation of
the Earth will cause the source to project different baselines at different times. tracing
an elliptical path across the (u. v) plane. One can also increase the number of acuia]
physical baselines by moving one antenna relative to the other. thereby changing the
value of L. By measuring the complex visibilities at each point. one can construct
an image if sufficient areas of the (u. v) plane are covered. This method is called
aperture synthesis.
Since such a procedure is time consuming. one can speed up the process by hav-
ing a higher number of elements in the array. For example. a seven-element uniform
spacing array will provide six baselines at IL. 21.. 3L. 4L, 5L. and 6L. where L is
the spacing between two elements. However. by placing the elements at nonuniform
intervals. all six baselines can be reproduced with only four elements. with separations
of L. 3L. and 2L between adjacent elements (Fig. 3. 10). Such a configuration is called
a minimum redundancy array. Because the cost of the array increases with the number
of elements. a nonuniform array is obviously more desirable than a uniform one. Fur-
ther increase of the number of baselines can be achieved by creating stations along a
railroad track and rotating the antennas to different sets of stations. This allows a more
complete coverage of the (u. :1) plane than relying on the r0tation of the Earth alone.
For example. the VLA has 27 antennas along three arms. but has 4 x 27 number of
stations. For extended sources where a larger beam is preferable. a Set of stations with
shorter baselines is used to form a compact array. For small sources where maximum
resolution is needed. a set of stations with long baselines is used to form an extended
array. The nonlinear nature of the array also allows for more baselines. In the case of
the VLA, there are (27 x 26)]2 = 351 simultaneous and unique baselines. So even by
taking observations fora short duration oftime (called a“snapshot”). there is adequate
 3.3 Spectroscopy 73

OwL—Ofi at G 2:. Q
41.

.IL __
:7 5!.
#— 6L

Flgrtre 3.10
By using nonunifonn spacings. six baselines can be achieved by four elements.

coverage of the (u. v) plane and a reasonable image can be obtained. For relatively
bright sources where an 3-hour integration (time needed for a full synthesis at the
VIA) is not required, the “snapshot“ provides a time-efficient alternative.
With the use of interferometers, more and more small angular-size objects are
becoming resolved. The measurements of intensity are approximated by the measure—
ments of flux over different angular scales with a combination of different baselines.
Due to the finite number of baselines, interferometers often miss parts of the flux. so
a single-dish measurement of the total flux (or so-called zero-baseline flux) is needed
to complement the interferometer measurements.

3.3 Spectroscopy
Due to quantum transitions. the flux of an astronomical object can change greatly
over small wavelength intervals as the result of line emission or absorption. This
necessitates the need to make flux measurements over very fine wavelength grids.
a pmtice known as spectroscopy. The ability to separate colors, lcnown as spectral
resolution, can be achieved by decreasing the wavelength interval AA through which
the flux is measured. Since there are fewer photons passing through a narrower
bandwidth. spectral resolution can be achieved only at the expense of sensitivity.
The actual observed spectrum of an astronomical source is a convolution of the
source's intrinsic spectrum I” and the instrumental profile ¢u- Even for a Spectral
line. the width of the line is not zero due to various broadening mechanisms (Section
5.8). In the limit where the source spectrum approaches a delta function, the observed
spectrum reflects the instrumental profile. In order to distinguish two spectral lines
near frequency no. the equivalent width of the instrumental profile. defined as

A”: M.
¢vu (3.52 )

must be smaller than the frequency separation of the two lines. The ability of a
spectrometer to separate closely spaced spectral lines is quantified by the spectral
molving power defined by
”0
R= (3.53)
Av-
74 Measurements of Radiation

High spectral resolutions are desirable for three reasons: (i) to separate the
blending of spectral lines. (ii) to determine the shape of the line profile (Section
5.8). and (iii) to separate kinematic components through the Doppler effect. Since
weaker lines are often blended with strong lines. they are revealed Only under high
spectral resolution. Astronomical spectroscopy can have advantages over laboratory
spectroscopy because the effect of thermal broadening of the lines in low-temperature
interstellar clouds is much lower than that under laboratory conditioas. A full solar
spectrum contains well over one million lines. approximately half of which an:
unidentified. The fraction of unidentified molecular rotational lines in a submm
spectrum of an emission nebula can also be very high (Section 7.4). Improved spectral
resolution is therefore the only way to detect the presence of low-abundance atomic
or molecular species.
The dynamics of interstellar clouds (expansion. collapse. rotation. etc.) can be
traced with changes in the profiles of emission or absorption lines. The velocity
resolution. given by the Doppler formula

Ail.
A v =——
A c. (354)
.

is directly proportional to spectral resolution. Mth typical heterodyne receivers.

specu-al resolution (Jr/AA) of >106 in the min/submm region is routinely achieved.
giving velocity resolutions of ~ 0.1 km s '.
One of the first spectrometers used was the grating instrument where interference
separates light into colors. In modern spectrometers. a grating is used to disperse light
onto a CCD detector through a rectangular entrance aperture at the focal plane of
the telescope. A spectrum is formed as light is dispersed along the long side of the
aperture. The variation of the spectrum as a function of position is obtained along
the short side of the aperture. In the case of a CCD detector. the spectral resolution
is determined by the dispersion properties of the grating as well as the size of the
pixels on the CCD. Echelle spectrographs use two separate dispersive elements (e.g..
gratings): one to separate different orders of diffraction and the other to disperse each
onto different parts of the detector.
With CCDs and interferometers equipped with spectrometers. imaging and spec-
troscopy can be canied out simultaneously. For example. if a nebula is mapped in a
specific spectral line. the images at different wavelengths will provide kinematic infor-
mation as the spectral line undergoes frequency shifts as a result of the Doppler effect.
These observations generate 3-D data cubes (although computationally intensive to
analyze). which can allow us to re-crcate the kinematic structure of the nebula.

3.4 Summary

This chapter is not intended to serve as a comprehensive treatment of observational

astronomy. Instead. it is presented to establish a link between the fundamental con-
cepts of intensity and flux with the observational techniques of photomtry, imaging.
and spectroscopy. Only through an understanding of how observations are obtained
 Exercises 75

can we correctly interpret the observed parameters. tie them to the radiation proper-
ties. and reveal the underlying physical processes responsible. Having established the
basics in fundamental concepts and observational techniques in Chapters 2 and 3, we
can now proceed to discuss the various radiation mechanisms that generate the rich
observational results from the ISM.

Further Reading
Krause. I. D. 1936, Radio Astronomy. Cyguns-Quasar Books.

The following two books contain comprehensive treatments of observational

techniques in astronomy:
Rohlfs, K.. and Wilson. T. L. 2003. Tools ofRadio Astronomy. Springer-Vedag.
Léna. P. 1988. Observational Astrophysics, Springer-Verlag.

Exercises

. Assume that the IRAS bandpasses have square profiles (051;) with widths of 8, IO.
40. and 40 um centered at ll. 25, 60. and 100 Iurn. respectively. Calculate the color
correction factors for a star with a spectral shape of a 10.000-K blackbody.
. A quasar is observed by a radio telescope to have a flux density of l .ly at the frequency
of 5 GHz. The angular resolution of the telescope is 0.] arcsec and the quasar is
unresolved (poinllilte) at this resolution. What is the minimum brightness temperature
of the quasar at this frequency?
. A circular source of uniform brightness Tb = 1 K of size l” is observed by a telescope
with a Gaussian beam profile:
4 .
C(p) = 1123.34" zlle’), (53.1)
rrB

where p is the angular distance from the beam center and B is the half-power width
of the beam. Calculate the values of TA for B = l. 2, 3. 5, and lo".
. A circularly symmetric source with a Gaussian brightness distribution of the form

to) = [oe'4'“2"”"°2) (53.2)

is observed with a Gaussian beam of the form in eq. E31. where a and B are die
full-width-half-rnaximum of the source and the beam, respectively. Calculate the flux
measured by the telescope.
. Show that the visibility function of a symmetric source with a Gaussian brightness dis-
tribution is also a Gaussian. For a Gaussian source with a half-width-han-maximum
of w,
{(6) = Io€_{lu $11582. (3.3)

show that the projected baseline L (in units of kl) at V = 1/2 is 45.3811) (arcsec).
76 Measurements of Radiation

Figure 3.11
'I\vo one-dimensional sources of same size and intensity are separated by a distance L.

Similarly. show that for a 2-D Gaussian source,

Lr(k)t)w(”) =6431n—2-
I 1:2

= 45.5 I. (53-4)
. Calculate the visibility curve of two uniform brightness sources each of size a sepa-
rated by a distance L (Fig. 3.1 I).
Him: The intensity distribution of two uniform brightness sources is equivalent
to the difference of two uniform sources of size a + L and L — a centered at x = 0.
. The visibility amplitude of a uniform brightness source is given by eq. 3.37. Using
eq. 3.34, show that the intensity distribution of the source is Fo/a.
. A one-dimensional source of uniform brightness is observed with a two-element
interferometer at a frequency of 5 GHz. If the first zero of the visibility function
is feund at a spacing of 500 m. whar is the size a of this source?
. Design a five-element minimum redundancy linear array. How many baselines are
there in this configuration?
4
Photoionization and
Recombination

Stars. powered by nuclear fusion. are the dominant source of energy in normal
galaxies. Most of the energy output of stars is in the form of radiation. Interstellar
matter. consisting of gas and dust. has to deriveits energy from stars. primarily through
the interception of the radiative output of stars. The precess of photoionization. where
bound electrons in atoms are removed to free states as the result of the absorption of
a photon. is an effective way to transfer energies from stars to the gas component of
the ISM. The energy of the stellar photon, after having spent part of it to overcome
the potential energy of the bound electron. is converted to kinetic energy of the free
electron. therefore raising the temperature of the gaseous component of the ISM.
In order for an atom in the ISM to radiate, it has to be first excited to a higher state.
This can be achieved through inelastic collisions between atoms and free electrons.
The most common element. H. however. has its first excited state at 10.2 eV above the
ground state. corresponding to an excitation temperature (eq. 2.33) of ~ E/ I: ~ [05 K.
This is much higher than the typical kinetic temperatures of the ISM. Even for
electrons with energies high enough to overcome this energy gap. the low densities in
the ISM imply that the excitation or ionizatiOn rates by electron collisions are much
lower than the spontaneous emission rate (see Section SJ 1) and the collisionally
excited atom will remain at an excited state for a very short time. As a result. the
population of an excited state of H is determined not by collisions from below. but
by the recombination between free electrons with protons to form a neutral atom.
and the subsequent electron cascades via spontaneous emissions (Section 5.5). The
ionization and the excitation states of the H atom can therefore be assumed to be
completely controlled by radiation processes.
Photoionization is the dominant excitation process for the ISM. A radiation
source is assumed to emit sufficiently high energy photons lo ionize hydrogen (H) and
helium (He) in the surrounding gas. The electrons ejected in the ionization process
provide a pool of kinetic energy for the collisional excitation of the heavy atoms.
which have low-lying energy states accessible by collisional excitation. Spontaneous
emissions from the various excited states of different atoms and ions are responsible
for the rich emission-line spectrum in the visible region.

77
78 Photaionizarion and Recombimrion

Although ionization balance in stellar interiors and atmospheres is maintained

by collisional ionization and three-body recombination though the Saha equation
(eq. 2.45). this is almost never the case in the ISM. Instead. ionization balance is
maintained by photodissociation and radiative recombination. which are the topics of
this chapter.

4.! The Hydrogen Atom

The H atom consists of a positively charged nucleus (proton) and an electron. when:
the electron can be in the ground state or any of the excited states. The quantum
state of the atom is described by the principal quantum number (n. from i to co),
orbital angular momentum number (2 < n). the magnetic quantum number (m =
0. :i:l. . . . . it). and the spin quantum number of the electron (s = :izl/Z). The
lowercase letters 5'. p. d. f. . . .are used to represent 2 = 0. l. 2. 3..... Forenample.
theground state oins ls (n = 1.1 =0),andthe firstexcited states ofHarleande
(Fig. 4.1). Since the only force in the system. the electromagnetic interaction between
the proton and the electron. is a central force. all the orbital angular momentum states
of the same principal quantum state are degenerate. The energy of the bound electrori
is a function only of n and is given by the Bohr formula

l
5,, =hRH (1— :2). (4.1)
where

ane‘m:
H= 1:3 (4-2)

is the Rydberg constant for H and

m' — ""m” (4.3)

e me+rnp

is the reduced elccu'on mass. mp is the mass of the proton. The Rydberg constant for
a stationary. infinitely heavy nucleus is given by

ane‘m,
Rm = h3 . (4.4)

For hydrogenic ions with a nucleus charge Z (e.g.. He+. Z = 2). the corresponding
Rydberg constant (R1) is obtained by substituting unip for the mass of the nucleus in
eq. 4.3.
Fromeq. 4.1. atransition froman upperstaten=i toalowerstateu=j will
emit a photon of frequency

1 l
v = RH (1T2 '- i—z) . (4-5)
 4.1 The Hydrogen Atom 79

E(eV)
s p d f 3 I4
n-4 ------------------------- 1
4r!
”-3 3d '2."

n=2 10—

fl—

6—.

4-

2—.

rr=l 0-

Flgure4.l
The energy diagram of the H atom plotted in columns of constant orbital angular momentum
quantum number (t). Arrows indicate some of the low-lying allowed electric-dipole transitions
satisfying the At = :t:l selection rule (Section 5.l). The two transitions (labelled by u. and v2)
connecting the 2.5 and Is states represent the two-photon process (Section 6.2).

The transitions corresponding to j = 1. 2. 3. are called the Lyman. Balmer. and

Paschen series. respectively (Fig. 4.1). For hydrogenic ions where the nucleus has
a charge Z. the corresponding formula is

v = ml (Ii: — '11). (4.6)

Because of the difl'erent values of R, for each element, the transition frequencies do
not coincide exactly with those of H. This allows their lines to be separated from H
in a spectrum.
If the electron is initially at. level at and a photon is absorbed by the atom. the
electron can be excited to a higher level n'fl’. or to a free state. The latter process is
referred to as photar'onr'zatr'on (or bound—free. b—f). Photoionization of the H atom
will occur if the frequency (v) of the incoming photon is greater than u,:

R
u" = :21. (4.7)

The Lyman limit (”I = 3.283 x 10” Hz) is defined as the minimum frequency re-
quired to raise an electron from the ground state of H to a free stale.11're excess
80 Piroroionizarion and Recombimtr‘on

energy of the photon after overcoming the ionization potential will be transferred to
the free electron in the form of kinetic energy:

I
im¢u2=hu—hvn. (4.3)

One can generalize the Bohr formula to include the continuum states by defining
a quantum number k. where n = H: and r' = J — l. The energy difference between a
bound state it and a free state it is then given by

l 1
Elm = hRH (F + F) . (4.9)

Comparing eqs. 4.8 and 4.9. we have

I it]?
Enter)2 = 72-11. (4-10)

4.2 Spectroscopic Notation

For a heavy atom that has more than one electron. the electronic configuration of the
atom can be specified by the quantum states of each of the electrons:

(H l31)q'(!1232)‘” - - - (”mim)“. (4-11)

where n is the principal quantum number, 8 is the orbital angular momentum quantum
number. and q is the number of electrons in each subShell. with E‘- q; = total number
of electrons. For example. the lowest state of He is Isl. where the leading numeral 1
indicates the principal quantum number n. s for the t’ a 0 orbital angular momentum
state. Due to the Pauli exclusion principle. the maximum number of electrons that can
occupy a subshell is (48 + 2). For the S subshell. the maximum number of electrons
is 2. and the next electron must go to the n = 2 state. Therefore. the ground states of
lithium (Li) and beryllium (Be) are ISZZS and 152252. respectively. Under the n > r
rule. electrons with orbital angular momentum C = l are allowed. so the ground state
for boron (B) is 1:2252p'.
The electron configurations of multielectron atoms can also be described by the
total angular momentum quantum numbers. Under Russell-Saunders (or L — S) cou-
pling. the electron configuration can be conveniently expressed in the Spectroscopic
notation n25+'L,. where n. S. L. and J are the principal. spin. orbital. and total an-
gular momentum quantum numbers. respectively. The term 25' + l is referred to as
the multiplicity. The permissible values of J determined by vector addition of L and
S are L + S. L + S — 1,...[L — SI. The parity of a multielectron atomic state is
determined by (—1)“. The parity of the state is indicated by adding a superscript
“o" for odd parity. For example. the lowest energy term of N with a configuration
 4.2 Spectroscopic Notation 81

of 1:22:22p3 is written as 455’”. This designation is needed because certain spectro-

scopic notations can arise from different electron configurations. For example. C2+
can be in the electron configurations 131stp or 1:22;)2. leading to 3P” and 3P states.
respectively.
With the use of the spectroscopic notation. we can construct the energy diagram
of He. which is in almost perfect LS coupling. The He atom has two electrons. which
can be in the S = 0 (antiparallel electron spin) or S = l (parallel electron spin) states,
corresponding to multiplicity values of I (singlet) and 3 (triplets). respectively. Due to
the AS = 0 selection rule (see Section 5.1). there are no allowed transitions between
the two spin states, and the singlet and triplet He can be considered to be separate
species. The energy diagram is usually arranged in columns of increasing L (see
Fig. 4.2). For the singlet state. the lowest energy level is 1'30. Other excited states

—24 E(eV)

21

20

l9

Flame 4.:
Entry diagrams of singlet (left) and triplet (right) He. The solid lines connecting various energy
levels indicate some of the allowed electric-dipole transitions with the corresponding wavelengths (in
A) labelled. The two transitions (dashed lines labelled by v, and ”2) connecting the 7.9 and Is states
represent Ihe two-photon procas (Section 6.2).
32 Phomionr'zarion and Recombination

of L = 0 (first column) are possible by exciting one electron to a higher In state. The
first P slate is ZIP. because rt > t and the p electron cannot be in the n = lstate. The
possible total angular momentum quantum numbers are IL — SI to It. + S |. or J = ]_
Similarly. the possible L = 2 states are 3‘02, 4'02. and so on.
For the triplet state of He. the lowest energy state is 2331. Because of the Pauli
exclusion principle. the two electrons cannot have the same quantum numbers. Since
they have the same spin quantum number. they must have different :1. The lowost state
in the L = lcolumn is 23F, with possible I values of“ — l] to I] + ll. orO. l, or2.The
Ca atom has two valence electrons and therefore has similar spectroscopic behavior
as the He atom. The lowest energy states of Ca are 4‘50 and 53$, for singlet and
triplet states. respectively. The energy diagrams (called Grotrian diagrams} of more
complex atoms can be found in chemistry handbooks. A list of the ground states of
neutral atoms and their ionization energies is given in Table All. We can see that all
the alkali metals (first column in the periodic table) have similar ground states (28m)
to H and all the inert gases (last column of the periodic table) have similar ground
states ('50) to He.
After He. the most common elements are C. N. and 0. Since the filled orbits
(1:2. 252) have no net spin or orbital angular momentum. the electron configuration
of these atoms and their ions can be described by their valence electrons. For example,
the ground states of C. N. and O are. respectively. 2:12. 2p3. and 2p“. The L5
combinations that arise from these electron configurations are called terms. Using
the rules of angular momentum addition and the Pauli exclusion principle. one can
derive the atomic terms. For example. in the p2 configuration. the two electrons have
individual orbital angular momenta of if. = 1. £2 = l. The possible values for L from
f. + £2 are 0. l. or 2. corresponding to S. P. and D States. Since the two p electrons
can each have spin of U2 or — U2. possible values for S are 0 and l.The possible terms
are therefore '50. 'PI. 102. JSI. 3PM} and 3DL2I3. The Pauli exclusion principle
dictates that no two electrons can have the same quantum numbers n. E. mt. and m,.
For the two p electrons in the same principal quantum state n. this means that they
must have different combinations of me (+1. 0. or — I) and m, (+ or —). By listing
all the combinations of mu. mu. "1,1. and "1,2. one finds that only the terms lS. ID,
and 3}" satisfy the Pauli exclusion principle. If the two p electrons are in different
principal states n. and n2. then all six terms ('so. '19.. 102. 35.. 390.2, and 30m)
are possible.
Similarly, the possible terms for p3 are 2P. 2D. and ‘5. When the number of
electrons fills more than half of the subshell (e.g.. p“). the combinations of L and
S available to these electrons are exactly the same as if the number of elecnons is
equal to the number of unoccupied substates in the subshell. Therefore. the possible
terms for p4 are exactly the same as for p2. namely. '3. 'D. and 3P. Examples of
atomic terms arising from p and d electron configurations are given in Table 4.1. The
transitions between levels in different terms make up a multiplet.
Since J = L + S. for each term. several values of J are possible. For example. the
3t” state for the ground state of C can have J = 0, l. and 2, resulting in levels of 3P0.
3P., and 3P2. respectively. These levels are split by spin—orbit interaction between the
 4.2 Spectroscopic Notation 33

Table 4.1
Atomic terms arising from p" and d" configurations

Electron configuration Terms

Pl‘ p3 2p

pz'pd IS,ID.3P

p3 2P. 20.45

d'. d9 2D
dlldl IS.'D.I'G,JP,]F

d3.d1 2P.20.1F.2G.1H.4P.4F

d“. d‘ 's. 1D. 'F. 'G. '1. 39.30. ’F. 30.13.50

d5 13. 2P. 20.15 10.2H.2l.‘P,‘D.4F.‘C-'.‘S

Source: Berth I995. Spectra ditto-nu and Molecules. Mic 5.6.

electrons (Fig. 4.3).' The transitions between these states are known asfine-structure
lines.
The relative energies of difierent terms under the same electron configuration
(e.g.. each line in Table 4.1) are given by Hund's empirical rules. in order of priority:

0 Higher S => lower energy

0 Higher L => lower energy
0 Higher J => higher energy if the shell is less than half-filled, lower energy if the
shell is more than half-filled.
0 If the shell is exactly half-filled (e.g., p3). the lowestenergy term is always S and
therefore has no spin-orbit splitting. For the other terms, the energy order does
not obey a simple rule. For example, the 2P term of Ne“ (with an electronic
configuration of p3) has the 2 P3,, level above the 2 PW, whereas the 2D term has
the 203/2 above the lbs/2.

When the first rule is applied to carbon. the lowest state is 3P. Since 1.5' and ID
have the same values of .S'. the second rule suggests that ID is below ‘5'. Within the
3? state. the lowest term is 3P0 and the highest term is 3P: since the p2 shell is less
than half-filled.

l. The orbital motion of an electron produces a current, which creates a magnetic field that can
interact with the magnetic moment of the electron spin. This is known as spin—orbit erupting.
 [P
I" h—
I 'D
,1 Ir .- _ IDZ
Sa0 I/
1 (Singlets) \
r \\ I
\ F .. _ IF!

. . Residual . -
Unpert'urbed state Spm—spm e!ectron—electron Spm—orbtt

'S
r '- _ “so
’ __-_’£ ______________ _. , PI
,1 1’-
5=o I”
': (Singlets) \\
l \ ID ‘
:
.l
-- D;
.l'
l
l
l'
l
l
I
l I
"P” P "
L 3.S'
\\ ’1------------------- JS'
\ I 3P __ _ 1

\\ 5:3 9’” ‘=-..___._¢', 3pm.:

“HPMSJ \\ JD "_~_____-_ 3

\- HHHHHHHH ;**:::::::::i DWI-l

Figure 4.3
Top: Schematic diagram illustrating the Splitting of energy levels of a 4p4d electron configuration
under L—S coupling. The interactions that Split the degeneracy are listed under the levels. Bottom:
Same as above except for two p electmns. The dashed levels are missing if the two electrons ate
equivalent (n = n') (adapted from Leighton. R. 1959. Principles ofMadern Physics. McGraw-Hil].
Figs. 3.1 and 3.3).
 4.3 Bound—Free Transition BS

We should note that Hund‘s niles apply only to terms with the same electron
configuration. For example, the two lowest states of triplet He 23S and 23? (Fig. 4.2)
arise from 1523 and 152p, respectively. and Hund's rules cannot be used to determine
which of these states has higher energy.

4.3 Bound-Free Transition

“18 CTDSS Sfltion (undid) for an atom in an initial state nf to be ionized by a photon of
energy in: to a free state of H’ can be calculated by the time-dependent perturbation
theory. The cross sections for hydmgenic ions of nuclear charge Z can be written in
the following form:

4mm“ n2 max(t 3')

a..:()
k1 = ( ——°
3 )ZZ,.=Zm
— 2z+1 (n £,K£’.)
—'@ ( 4.12 )
where

ems. K!) = (1 +n2K2) 13m, “of. (4.13)

z2 °°
guilt. K8,) = —2- Rn£(r)rFua(r) dr. (4.14)
n o
k
K=Ei, (4.15)

and
’12

do: 432m :2 (4-16)

is the Bohr radius. 8’ is the angular momentum quantum number of the ejected
electron. R,¢(r) and Fudr) are the initial and final normalized radial wave functions
of the ejected electron. and
2
a = L” (4.17)
he
is the fine-structure constant. The integral in eq. 4.14 can be evaluated numerically
to calculate the bound—free (b—f) cross section ((2,015)) for each energy level. For
historical reasons, these values are often expressed as the classical expression of
Kramers, multiplied by a correction factor known as the Gaunrfacror (gm-(n. 1.)):

unfit!) =
311225 R,z4 gb[(nL), (4.13)
3J3 ch3 n5v3
Where R, is the Rydberg constant for the hydrogenic ion 2.
06 Photoionization and Recombination

1‘2 T—Ij l—{I lj I 1 T' I r1 II’I’I 1—I7‘ I—IIF—fi‘j'firlTr

0.3
E
E
E
=

:3
.E'3
5 0.4

0-0 Ll_lLl_lt_lJ_lJJ_liJ_1Ll_lLl_LLl_I:‘P-I.LIAJJ[Ll-I.

-4.0 -3.0 —2.0 - l .0 0.0 1.0 2.0 3.0 4.0

Iog'otfiiecuon enemy (Rydbcl'gD

Figuretti
Variation of the bound—flee Gaunt factor as a function of frequency. '11: solid lines show the
Gaunt factors forn = l andn =2.Tbedashed linesshowdteconu'ibutionsfromdtezs and
2p states to the total :1 = 2 value.

We can also define the avenge Gaunt factor for each I: state as

"—1
sum) = go (3952.12) gflmL). (4.19)

Figure 4.4 shows the average Gaunt factors for the n = land n = 2 states of H. as well
as the oonuibtltions to m, from the is (223m) and 2p (22P.,2_,,,) states. We can
see that the Gaunt factor varies slowly with frequency, and the frequency dependence
of the cross section is mainly determined by the 1.!“3 term.
 4.4 Bound—Free Absorption in a Stellar Atmosphere 87

Expressing the photon energy in units of ultra. we can rewrite eq. 4.18 in the
form

64 ,, 3
a,,(u) = [first] (1103)" (v?) gbftn). (4.20)

The numerical value of the constant in square brackets in eq. 4.20 is 0.09, so the b—f
cross section is approximately 1110 of the geOmeu'ic cross section of the H atom. At
the Lyman limit. gMUs) has a value of 0.7973 and the b—f absorption coefficient for
the ground state of His) is 6.3 x 10'lEl cmz. The mean free path for a photon at the
Lyman limit is

l
l “H — (4.21)
"1:01:00
5 x 10-2
.. __ , 4.22
(n ”fem—3) PC ( )

where n], is the number density of H atoms in the ground state. Provided that most H
atoms are in the ground state (n I: = It"). a Lyman continuum photon will travel only
5 x 10-2 pc before being absorbed by an H atom even with it“ of 1 cm".
The corresponding optical depth over a distance of L is

r = nbabwfll. (4.23)

~ 190: u/"H)("H/Cm_3)(L/PC)- (4.24)

Since interstellar distances are typically many pc. the interstellar medium is always
"cloudy" unless the gas is highly ionized by other means (it ”In" << 1). Although
the photoionization cross section is not much different in the visible, the number of
b—f transitions from the excited states of H is small because of the low populations
in the excited states. This makes the mean free path for visible photons much longer
and allows visible light to travel much farther than UV light. The fact that we can see
stars at night is a testimony to the assumption that very few H atoms in the interstellar
medium are in an excited state.

4.4 Bound—Free Absorption in a Stellar Atmosphere

in a high-density environment (e.g., stellar atmosphere) where the excited levels of

the H atom are populated. the total absorption coefficient due to the b—f process can
be calculated by summing the absorption by H atoms at each state:

xv = Znnanw). (4.2s)
Pkaroionizalion and Recombination

If the H atoms are in LTE. then their population distribution is given by eq. 2.42:

"n
— = ——e
252 —E" m' . 4.26
l"H ZH(T) ( )
At low temperatures, (Es/H << 1 and all the higher terms in the partition function
(eq. 2.4l) can be ignored. In this case. ZH : g. z 2 since the electron in the ground
(15) state can be either spin up or spin down. Substituting eq. 4.26 into eq. 4.25. we
have
32 H2e6 e—hvlll'T W

= ——-————R E l
_ r. Val" gbfol) . 4.27 i
xv 31/5 Ch} ”3 HRH n38 (
n=n’

where n’ is the lowest value of n that satisfies v“: < v. Since an H atom at level n can
be ionized by a photon only with v > u". the total b—f absorption coefficient takes
on sudden jumps at frequencies of up v2, and so on. These discontinuities. occurring
at 912. 3646, and B204 A are referred to as Lyman. Balmer. and Paschen jumps,
respectively. From eq. 4.20 we have

“—"(E ~_~ n, (4.23)

“10“)
neglecting the differences in the Gaunt factors. Therefore the b—f absorption coeffi-
cient at the Balmer edge is two times higher than that at the Lyman edge.
Since the upper levels ofthe H atom are closely spaced. the summation in eq. 4.27
can be approximated by an integral:
9" co
2 lam/tr 2 _l f €153,000 K/nsz l
n3 2 "r rt2
nan'

T 0
e” dy
- 3053.000 K) j;
_ L [ea — l]. (4.29)
‘ 316.000K
where y = 153,000/n2T and a = 153.000/n'2r. For T =10*1 K and n’ = 10. the
integral above gives a value of 5.4 x 10—3 compared to the actual sum of 6.0 x 10—3.
Fora photon of v. > v > v2. 7: = 2 and n = 3 terms of the sum give values 0f6.5 and
0.2. respectively, showing that the lower states dominate the contribution to the b—f
absorption coefficient at low temperatures.
The b—f absorption coefficient for other H-like elements (e.g.. singly ionized He)
can be similarly derived. The energy level for an H-like atom with nuclear charge Z is

2nrze“m;22 1
 4.5 Recombination B9

and the corresponding values for 11,. are

2:12:41“; 22
U": (4.3!)
)9 rr2 .

We can see that the Lyman (v1). Balmer (v2). and Paschen (v3) jumps of H correspond
to the n = 2. 4. and 6 jumps of He+ (Z = 2). other than small differences in the
reduced masses mg. The b-t' absorption coefficient of He+ therefore has twice as
many discontinuities as H.
In deeper parts of the stellar atmoSphere. H can be ionized by collisions and the
fraction of neutral to ionized H is given by the Saha equation. From eq. 2.45, we
can see that the ionized to neutral ratio is very sensitive to temperature. At an electron
pressure (P. = rick T,) of l dyne cm‘z. the transition from neutral to ionized H occurs
at ~ 8000 K. While we can assume that the b—t' contribution to the total opacity is
zero in a totally ionized region. in the transition region. eq. 4.27 has to be modified
to include the fraction of H in neutral form (nH/(nfl + n A,)). which can be calculated
from the Saha equation.

4.5 Recombination

The energy of the free electr0ns created by photoionization is dependent on thcenergy

of the stellar photons. However. these electrons thermalize very quickly because of the
very large electron-electron collisional cross sections. Although low-energy electrons
are more likely to recombine with protons (eq. 4.39) and are therefore selectively
removed from the free elecuon pool. the recombination rates (eq. 4.47) are very
slow in comparison with the interactions among electrons themselves. It is therefore
an excellent approximation in the nebular model that the electrons are in LTE and
their energy disuibution can be characterized by a single parameter 1",. the kinetic
temperature of the electrons.
Since both the photoionization cross section (an,(v)) and the recombination cross
sectiOn (Una) are atomic parameters. their values are independent of environmental
conditions. We can therefore derive the relationship between these two parameters
under the principle of detailed balance. which connects a microscopic process with
its corresponding inverse process. One of the most well-known examples for the ap-
plication of the principle of detailed balance is the balance between atomic absorption
and emission processas (Section 5.5). In the present case. the principle of detailed bal-
ance requires the photoionization rate of a neutral atom in excited state at to be equal
to the recombination rate by electron capture.

4rrnnLanL(v)Bv(T)(l — e-*“/”):—” = npn,a.L(u)f(u. T)v dv. (4.32)

U
90 Photaionimttbn and Recombination

where on L is the recombination cross Section from a free state to level (n L), and f (u)
is the Maxwellian disuibution (eq. 2.37) of electron velocities at temperature Tc:

4 3’2
f“) = E (£-—;) v2e_""”z/ur'. (4.33)

The factor (1 —e "”’"“T) in eq. 4.32 is to account for the effects of stimulated
recombination in thermodynamic equilibrium.
Under thermodynamic equilibrium conditions. the number density of neutral H
atoms in the ground state (is) is related to the proton (up) and the electron density
01,) by the Saba equation (eq. 2.45). For H+. there is only one configuration. so
the partition function is equal to l. The equation for the ionization balance for H is
therefore
2 312
”U =( h ) aha/"T. (4.34)
npn, 21rmekT

The population in an excited state (:1. L) is given by the Boltzmann equation:

m = n1,(2L + or M". (4.35)

The factor 2L + l is due to the fact that each L state has 2!. + lsubstates. Combining
eqs. 4.34 and 4.35. we have

nu =npn.t2L + 1) (2” H)
(:2 3” aha-l”. (4.35)
e

Substituting eqs. 4.36 and 4.33 into eq. 4.32. and making use of eq. 4.8 and its
derivative w.r.t. v.

hdu =mev du. (4.37)

we have

a"L(v) _ 1 ӣ31!ch
_ —-———. 4.38
a"L(u) 2(2L + I) hzuz ( )

Substituting eq. 4.18 into eq. 4.38, we have

_ 16 ezh v, hvl 2L+l)

0,1,0” — (ST/=5?) (-1?) (gm) (T gbf(nL). (4.39)

We note that this relationship is true whether the atom is in LTE or not. The constants
in the first parenthesis have a numerical value of 2.105 x 10‘22 cm2. Since the other
three terms in parentheses are all of the order of unity. the recombination cross sections
are therefore much smaller than the geometric cross section of the H atom.
 4.5 Recombination 91

Making use of eq. 4.19. we can write an expression for the recombination cross
section to level n:

_ Iii u) Gm“):
iv. (1)
U..(v)-(3‘/jmgcfi)(u n, and"). (4.40)

For an ensemble ofelectrons with a velocity distribution obeying the Maxwellian

distribution, the recombination process can be characterized by a single parameter T,
rather than individual electron velocities 0. We can therefore define the recombination
coefficient as the recombination cross section to level nL averaged over the entire
electron ensemble:
oo

aMITe) =10 UnvaW) dv. (4.41)

Substituting eqs. 4.33 and 4.39 into eq. 4.41, we have

and ').-_ —— = _.) (—) {-1 _.

a 16 22h
fi(3\/§m3c3) (fin)
m ”2(hv 1 2L+l

3/2
m, n5 gbfe
OD —:
;_
we"
J: x

= 3.3 x 10‘'2 cm3 s‘I (fl) (2L + 1) gbfec'f €— dx. (4.42)

T, n5 n I

where

c. = k2,} = 52% (4.43)

and

m t.-2
x = 2:1; + g". (4.44)

The total recombination coefficient is the sum over captures to all states:

on n—l

at = Z: Z cram). (4.45)
11:] L=0

For Te =10“ K. a,‘ for H has a value of 4.13 x [0‘13 cm3 s". The time scale
for recombination can be estimated by

1
l',= (4.46)
"(all

~ 7.6 x 104 (4.47)

(ac/c1114) '
92 Photaionizarion and Recombination

The recombination time scale is relatively short in comparison to typical dynam-

ical time scales (Chapter 15) under high nebular densities. Under such cases, the
ionization—recombination problem can be treated as a time-independent process.

4.6 Ionization Structure of :1 Static Nebula

Let us consider a nebula whose ionization suucture is maintained by the UV photon

output from a single central star. as in the case of an H [I region or planetary nebula.
If the recombination time is short compared to the dynamical time. the nebular
ionization structure can be assumed to be static. Since the recombination rate is much
lower than the spontaneous decay rate (Section 5.1 I). the H atom will quickly cascade
to the ground state after each recombination. and practically all neutral H atoms can he
assumed to be in the ground state. At each point in such a nebula. the photoionization
rate from the ground state is balanced by the total recombination rate to all levels of
the H atom:

an]? flav(ls)dv=npnneaAUL). (4.43)

where J, = f [grim/4n (eq. 2.20) is the mean radiation intensity at that point.
However, every recombination to the ground state will create another Lyman
continuum photon. which can be absorbed by another nearby H atom. If the nebula is
ionization bounded (i.e., no Lyman continuum photons escape). the recombination to
the ground state has no net effect on the overall ionization balance of the nebula. Since
the mean free path of these diffuse Lyman continuum photons is short (see eq. 4.22),
their existence can be ignored by not counting the ground state in the recombination
process. In other words. the total number of ionizing photons entitled by the star of
temperature T, and radius R,.

a= f 0° 47rR31r
m hu
3.0;)
d u. (4.49)

should be balanced by the total number of reeombinations to excited states (n > 1)

within the ionized volume.

Q = f npneag dV, (4.50)

where
W )I-l

a3=ZZan.(r) (4.5:)
n=2 [=0

is the total recombination coefficient to all but the ground state.

At T, = 10.000 K. as has a value of2.59 x 10-13 cm3 s- 1. Solving the equation
of transfer (eq. 2.67) together with the ionization equilibrium equation (eq. 4.48)
 4.6 Ionization Structure of 0 Static Nebula 93

shows that the H atom is nearly completely ionized out to a critical radius 1",. at which
the ionization state changes to neutral over a very short distance. In other words. inside
r3, "p = n, = n". and outside 1",, n P = n, = 0. In this case, eq. 4.50can be integrated
to give

Q = —rfnflaa, (4.52)

and r, is referred to as the Stromgren radius. and can be found as follows.

Since the total Lyman continuum photon output requires an integral. we can
separate eq. 4.49 into a physical part and a dimensionless numerical pan G(T..) by
introducing a dimensionless variable x = h u/ H}:

31:13: it?”
Q= C2 " (—
h ') 60..) (4.53)
where
on 2
G(T..)= ‘ dx. (4.54)
gt e" — i

It is easily seen that the value of G monotonically increases with T... If the star radiates
like a blackbody. the total stellar luminosity is

L, = drrREa'Tf. (4.55)
This allows us to express eq. 4.53 in terms of the stellar luminosity
[56(T_) (4.56)
Q= L..
:r‘UtT,
and to derive an expression for the Stromgren radius from eq. 4.52:

450(T.)L. l
= —— . 4,
r’ [47rskT*nfia3(Te)] ( 57)
Figure 4.5 shows the Stromgren radius as a function of T‘ for a star with L, = 10‘
L0 and three different nebular densities.
Assuming that the nebular dynamical time and the evolutionary time for the
cennal star are long compared to the recombination time, the ionimtion structure
of the nebula can be calculated for He and heavy elements. An atom X of atomic
number N has N + 1 ionization states, and the abundance of each ion (X‘) in each
part of the nebula is determined by the balance of photoionization and recombination
from the next (1' + l) ionization state:

Numflm W4 :21)! (X‘+1)n xfm f(v)uaj(v.Xi)dv.

U 0
’+' (4.53)
94 Pharoionizatian and Recombination

1-5 c l ' 1 - I ' l ' l '

[.4

1.2

1.0

r,(Pc) 0.8

0.5

0.4

0.2

0.0
[0.000 20.000 30.000 40.000 50.000 60.000 10.013
T-(K)

Figure 4.5
The Sufimgren radius as a function of stellar temperature for a stat of luminosity 10“ Lo
embedded in a nebula of densities Ill]. son, and NI!) cm 3.

where NJ- is the number density of the ion in the jth excitation state (j = l is the
ground slate). Here we have assumed that the rates of collisional ionization and
excitation are negligible and all photoionizations occur from the ground state.
Since each emission line comes from one ionization state of an atom, an accurate
ionization model is necessary to correctly deduce the total elemental abundance from
the strength of one line. This requires a good knowledge of the photoionization and
recombination coefficients, which can be difficult to obtain for complex atoms.

4.7 Diffuse Interstellar Radiation Field

In cases of diffuse clouds or reflection nebulae where there is no central imtintion

source. the ionization state of the nebula is detennined by the UV continuum from
diffuse starlight or cosmic rays (Fig. 1.8). A simple approximation to the energy
density of the diffuse interstellar radiation field in the 1912—3000 A region is

at = 4 x 10‘” erg cm'u-l, (4.59)

 4.7 Diflirse Interstellar Radiation Field 95

which is commonly referred to as the Habing radiation field. Using eq. 2.22. we can
express eq. 4.59 in terms of photon flux:

% = GOG/A) photons cm'2 see'l Ar]. (4.60)

In frequency units, eq. 4.60 is

4%” = 2 x rowel/AP photons our2 soc-1H2“. (4.61)

where we have made use of the identity v}, = 11;.

Another commonly used approximation to the diffuse interstellar radiation field
in the wavelength range of A = 912—2000 A is given by

4“" = A(A/A)_l — sum-2 + cot/AW photons orn-2 soc“ Hz". (4.62)

where A = 1.068350 x 10—3. B = 1.719258. C = 6.853491 x 10‘”. This is known

as the Draine radiation field. The Draine and other approximations to the interstellar
radiation field are given in Figure 4.6.
Intensity (105 ph cm 2 s" A-')

Draine J

Figure 4.6
Approximations to the interstellar radiation field in the nearulu'aviolet. The four curves are due
to Hahing. Draine. Mathis er at. (M) and Gondhalckar er al. (GPW) (from van Dishoeck.
E. F. 1988. Rare Coefl'kients in Aslmclrzmisrry. eds. T. J. Miller. D. A. Williams. p. 49).
96 Photar'om'mn'an and Recombination

4.8 Ionization of Complex Atoms

In addition to H. photoionization can occur from the ground state of more complex
atoms. For example. N I can be photoionized to a number of states of N tr:

N*(2322p2 3?) + e- iw > 14.5 eV

N(2522p3‘S3_,2)+hv » N+(2522p2ID)+e" h» > 16.4 eV (4,53)
N+{2522p2 13) + e' Irv > 19.6 eV

The cross sections at the photoionization threshold for the three processes above
are LB x lo '3. 2.5 x 10"", and 1.5 x 10 '9 cm2.respectively.WhiJetl'iephotoio1-..
ization cross section of H has the simple v ‘3 dependence. 0, of complex atoms
have more complicated structures (Fig. 4.7). In pam'cular. the presence of resonance
features (e.g.. those seen in Fig. 4.?) suggests that an ion can make significant con.
tributions to the optical depth of the nebula at specific frequencies in spite of the
low abundance of the ion. For simple atoms. interpolation formulae can be used to
represent the smoothed photoionization cross sections. For example. for C“.l —> C+,

a). =a‘h{t.|rxI + (I -- (ILIJHI. (4-64)

where a", =12.19 x 10 '9 cm1,)t,h = 1102 A, x = We. a = 3.317, and s = 2.0.

l I I 17 T
rrr‘rl'nn—I'Inr

lilllllllll
Theory (convolved)
GAME!)
3

II
IIII‘IIIIIIIII

ILILLlllllLLll

Experimental

_l_l__l I_l 1_1_J_J__L _l_l I 1

24 26 23 30

Figure 4.1
Comparison of d1eoretical (tap) and experimental (bottom) photoionization cross sections of
the ground state of C+ (NahaI. SN. 2002, Phys. Rev. A. 65. 0527M].
 4.9 A Dielectronic Recombination 97

Substituting the value of the photoionimtion cross section into the formula for the
photoionization rate of an atom yields
W

R,- = I flew. (4.65)

0 III!

and assuming the Habing field. we can derive the photoionization rate of carbon in the
interstellar diffuse radiation field tobe R,- ~ 1.8 x 10‘"J s' 1. Neutral carbon therefore
will be photoionized in about I ~ l/Ri ~180 yr. Most of the interstellar carbon atoms
are therefore expected to be in ionized form unless they are shielded from UV radiation
by dust (Section 14.3). The wide presence of C+ is confirmed by the prevalence of
the IST-um (3* line in the [SM (see Fig. LB and Section 5.3).
For the photoionization of sulphur (8° —> 3+), the photoionization cross section
can be approximated by

0,. = am[ax‘ + (3 - 2£I)J:'"l'l + (l + a — fl).r'+2], (4.66)

where am = 12.62 x 10-“ cm2. at”, =1193 A, a = 21.595. p = 3.062. and s = 3.0.
Under the Habing field. R ~ 2.2 x 10“'3 s“ and sulphur is again expected to be in
ionized form in the ISM.

4.9 A Dielectronic Recombination

Recombination of multielectron ions is much more complicated than thatof H because

of the presence of other bound electrons. For example, the direct capture of a free
electron to the innermost unfilled electron shell has to satisfy the Pauli exclusion
principle. The recombination coefficient can be much higher at certain energies (called
resonances) if the energy of the incoming electron corresponds exactly to the energy
of a doubly excited state of a bound level of a lower ionization state of an ion. This
ion can then radiatively decay to a singly excited state and then to the ground level.
As an example, the main recombination for doubly ionized C follows the process

c++(2_s’) + e'(0.4leV) -» C+(2.t'2p. 3d)

—. C+(2.s2p2) + hu
—> C+(2522p) + hv. (4.67)
where the free electron excites one of the bound electrons to the 2 p state while it settles
into the 3d shell. The resultant singly ionized C then undergoes two separate duays
to retum to the ground state. This prooeSS is referred to as dielectronr'c recombination.
The total recombination coefficients including the efiects of both radiative and
dielectrortic recombinations for multieleetron ions such as Si and C have been calcu-
lated using a unified o'eaunent. Figure 4.3 shows an example of such results for 0‘”.
The “humps" in the recombination coefficient at high temperatures are the result of
dielectronic recombination.
98 Pkotaionimtion and Recombination

10'9 WWW—WWW

e + 0 w —) 0 it!
I.

10-10 _—

§
"E 10'“ I"
3 .—

a“ I
7

IO'" :-

10 100 11110 l0.000 105 IO‘ [07

71K)

figure 4.3
Theoretical recombination coefficient (solid line) for 0H. based on a unified treaurtent. The short
dashed line (labelled 1) represents earlier results for radiative rates, the dotted line (labelled 2) for
low-temperature dielectmnic. and dashed (labelled 3) and dot-dashed (labelled 4) lines for high-
temperature dielectronic recombination rates (adapted from Nahat. S. N. 1999, ApJS. 110. ll”).
 4.]! Summary 99

ctions
4.10 Charge-Exchange Rea
Recombination of certain doubly and more highly charged ions A” can take place
via charge exchange with neutral H or He:

A” + n —> a“! ]+ m. (4.68)

Usually the ion recombines to an excited state and decays rapidly by spontaneous
emission. Consequently, the reverse process is not important. An example of the
charge-exchange reaction is

N+3(252J 's + H(ls) 2s -> N*1(‘Zsz3s) 2s + m“. (4.69)

which has a rate of 2.93 x 10 '9 cm3 s'l at T, = IO‘ K. Sometimes the electron
captured to the valence orbital is accompanied by a rearrangement ofthe core orbitals:

N++(?.sz2p) 2P + H05) 2’3 —» N+(2szp3) 31) + at (4.70)

which has a rate arose in: 10-9 cm] s" at r, = IO‘ K.

In ionization equilibrium models. the charge-exchange rates can simply be added
to the photoionization and recombination terms.

4.11 Summary

Photoionization is one of the major avenues of transferring radiative energy of stars

to gas in the ISM. Photoionization can occur in the vicinity of stars (e.g.. in H u
regions). in the diffuse ISM by absorbing diffuse starlight. or around the accretion
disks of black holes. such as in active galactic nuclei. The kinetic energy of the ejected
electrons is a major factor in the heating of the gaseous component of the ISM. and
this will be discussed in Chapter 6. Because the ionization potential of H is 13.6 eV,
photoionization of H from the ground state is the main source of opacity of UV light
in the Galaxy.
The ionization state of an element (neutral. singly ionized. doubly ionized. etc.) is
the result of balance between photoioniaalion and recombination. The recombination
process (direct or dielectronic) is dependent on the kinetic energy of the free electrons.
Recombination is also a major source of excitation of atoms and ions. in particular for
H and He. which have no low-lying energy levels available for collisional excitation.
The recombination to a high energy level and the subsequent cascade to the ground
state create a series of line radiation. with the consequence of converting the high-
energy continuum radiation of stars into low-energy line radiation. Since much of the
[SM is Optically thick to UV photons but optically thin to optical-line radiation. the
photoionization—recombination process creates one of the ways for stellar energy to
escape from the Galaxy.
too Photoiom'zation and Recombination

Further Reading
Ostet'broclt. D. E. l939. Astrophysics of Garcons Nebulae and Active Galactic Nuclei,
University Science Books.

Resource Materials

TIPTOP‘bas-e is an interactive database that allows access of atomic data computed

under the Opacity Project and IRON Project. It is available at NASA Goddard Space
Flight CenteriHigh Energy Astrophysics Research Center (http:/ll'teasarcgsfcmsa
.gov) and at the Center de Donnees Astronomiques de Strasbourg (httpfllvizier
.u-strasbg.frIOP.html).

Exercises

. Write down the ground-state electron configuration of the first 10 elements in the
periodic table. Use the spin and orbital quantum numbers of the valence electrons to
derive the spectroscopic notation of the ground state as shown in Table A2. 1.
. The total number of Lyman continuum photons emitted by a star is given by eq. 453.
Show that

G(x,) = Z ‘3" (n’xf + 2n. + 2) . (54.1)

where x] = h v] / H}. For a low-temperature star. the value of1. is large and this series
converges rapidly due to the exponential term. For a high-temperature star (1'1 << I).
it is easier to calculate the complementary integral

F( I 1) = j; 1' 6—]
‘2 dI
on 12
:10 e: _ 1 dz — G(x.). (E42)

Show that F (00) = 0(0) = 2; (3) and for small values of 11,

I 1 1'2 .I."
F ~2 ___I+_I__I , 54.3
(1') x1 [2 6 4a 4320 ( )
Use numerical integration to evaluate F(xl) and estimate the value of 11, for which
eq. 54.3 is in error by l%.
. A stellar wind with density distribution :1 (r) = 1100'] r0) ‘2 is being ionized by a central
star with a total Lyman continuum photon output of Q. Calculate the number of
 Exercises 101

ionizing photons remaining as a function of radius and find tlte minimum value of
Q for which the entire stellar wind is ionized. For Q smaller than this critical valueI
show that the Stromgren radius is given by

r ———'°— (E44)
3 1—9/9]. '
where Q. = 43rrgn3a3.
For a star of temperature 50,000 K and a luminosity of 50.000 LO. calculate
the maximum mass loss rate of the stellar wind that can be fully ionized by the star.
Assume the stellar wind begins at the stellar surface, has a gas temperature of 10,000
K. and is expanding at a speed of 2,000 km s‘ '.
. Calculate the wavelengths of the Lyman lines of H up to n = 20 and compare the
results to the observed wavelengths in Figure 5.3.
. Calculate the fraction of H atoms in the first excited state (n = 2) at temperatures
T = 5000, l0,000. and 20,000 K. Assume that the H atom is in LTE and approximate
the partition function by sununing up to n = 20.
. Assuming that the ISM has a density of n" = 1 cm'3 and a temperature of [0.000 K,
calculate the absorption coefficients and mean free paths of photons at the Balmer and
Paschen limits. Assume that the H atom is in LTE. g.»- = l, and include absorption by
H to levels up to n = 20.
. How many BO stars (Toff = 30,000 K. L = 60.000 L9) will be required to produce a
Stromgten sphen: of the same size as a single 05 (Ten = 42,1130 K. L = 900,000 L0)
star?
,4
Line Radiation from Atoms
and Ions

Astronomical atomic spectroscopy began with the discovery by Fraunhofer of dark

lines in the spectrum of the Sun. The comparison with laboratory measurements led
to the identification of these dark lines as absorption by atoms and the discovery of the
element helium. a chemical element first found in a nonterrestrial environment. This
fimtly establishes that the stars and theEanh share the same basic ingredients of matter
and provides the foundation of our belief that the laws of fundamental physics derived
in laboratories on Earth can be applied to distant stars and galaxies. The application
of atomic spectroscopy to astronomy represents the beginning of the discipline of
astrophysics.
While stars show a continuous spectrum superimposed with absorption lines, the
optical spectrum of an emission nebula is dominated by emission lines. The spectra of
quasars and active galactic nuclei are also dominated by emission lines. Line emission
occurs when atoms or ions make a transition from one bound electronic state to another
bound state at a lower energy. Such transitions. usually via spontaneous emission. are
referred to as bound-bound (b—b) transitions. In the interior of stars, electrons in an
atom aredistributed over many energy levels because of the high particle and radiation
densities. The bound electrons are excited either by free electrons colliding with the
atom. or by absorption of a photon. However. in the interstellar medium, both the
particle and radiation densities are low. and the population distribution of the bound
electrons can deviate greatly from the thennodynamic equilibrium condition given
by the Boltzmann equation (eq. 4.35).
The typical energy separations between the electronic states of atoms are of the
order of 1 eV. conesponding to photons in the visible or UV parts of the spectrum. The
only available visible or UV background in the interstellar medium is from diluted
starlight. which is generally not strong enough for excitation by photon absorption
to be significant. Therefore. the only way that a bound electron can be found in an
excited state is by collisional excitation from a lower state. or as a consequence of
recumbination between a free electron and an ion. The line photons entitled as the
result of collisional excitation are called collisionaily excited lines, and those emitted
following recombination are called recombination lines. H and He. with large energy
gaps between the first excited state and the ground state. are difficult to excite by

103
104 Line Radiatianfmm Atoms and Ions

collisions. whereas heavy atoms. with their more complicated electronic structures_
often have low-lying electronic states within fractions of an eV from the ground State.
and can be more effectively excited by collisions.
Atoms in the first column of the periodic table (called the alkali atoms) have
one valence electron and have energy structures similar to that of H. The sodium D
lines (IF-m —2S.I,.2 at 15890 A and 2P,,1 ‘231/2 at 5896 A). first observed in the
Sun by Fraunhofer. correspond to the Lya transitions of I-I.I For potassium (K), the
corresponding transitions are 10664.9 A and 7699.0 A. Early studies of neutral atoms
in the interstellar medium were based on several strong optical resonance lines (e.g.,
the Na 1 D lines). Most of the strong resonance lines of abundant species lie in the UV,
For example. the absorption lines of C I and 0 I have been detected in BD +30“3039
by the lUE and the Hubble Space Telescope (HST).
With the development of radio astronomy in the l9505. the All-cm hyperfine
transition of H t has been extensively used to probe the neutral atomic component of
the ISM. This line is widely observed in the Galaxy and can be used as a tracer of the
galactic rotation. In external galaxies. the H r line is often detected beyond the stellar
disk.
Since the 19705. space-based telescopes with spectroscopic capabilities have
opened up the possibility of observing electronic transitions of atoms and ions from
X-ray to the submm parts of the spectrum. These make possible the observations
of transitions that are difficult or impossible to study in the laboratory. including
transitions in highly ionized states of atoms and transitions from metastable states
with very long lifetimes.

5.1 Permitted and Forbidden Transitions

The selection rules in L—S coupling are

- AL=:l:lorO.
0 A320. and
0 AJ=0.ilexceth=0->O.

Since the emitted photon carries angular momentum, this requires at least one electron
to change its angular momentum (A8 = d: l, which is equivalent to the parity selection
rule of even 4-» odd). The A5 = 0 rule implies that transitions will occur only between
terms ofthe same multiplicity. In the case of He. which is in near-perfect L—S coupling.
transitions will occur only from a singlet state to another singlet state or a triplet state
to another triplet state. Since the transition from the lowest energy state of triplet He
(2351) to the ground state of singlet He (1'50) violates both the AI. = :l:l and AS = 0

I. In optical astronomy. the transitions are usually listed as lower state—upper state because 11'8-
ditionally they are observed in absorption in stellar atmospheres. In this book. our subject is the
interstellar medium and the lines are generally seen in emission. so our convention for transitions is
upper state-lower state.
 5.} Permitted and Forbidden Transitions 105

selection rules. the 235. state is highly metastable and has alifetime exceeding 2 hours.
Consequently, the 233, state can be treated as a pseudo ground state. and the transition
23? — 238 is analogous to Lya of H (Fig. 4.2). TransitiOns from singlet to triplet states
of ions of light elements such as C 111. 0 III. and N W (e.g.. 1s2 2s2p 3‘P — 1:1 2.52 ‘S
at 11906 A, 11908 151 of Cut) are referred to as intercombination transitions and are
only semi-forbidden because the ions are only close to L—S coupling. These lines are
indicated by a bracket on the right-hand side (e.g., the 11190711909 lines of C tit],
Fig. 5.1).
The strongly allowed transitions to the ground state (e.g., the 2P3); 35“;
15390 A and 1pm ism 215396 lines of Na 1 and the 2pm Is...2 13934 A and
2P”: 2511‘! A3963 lines of Ca II) are known as resonance lines. Permitted and
intercombination lines of C. N. O. and Si lie primarily in the ultraviolet. In Table 5.1.
we list some of the lines detected by the International Ultraviolet Explorer (IUE).
This list includes permitted lines. intercombination lines (AS at 0). and forbidden
lines (A3 7E 11). The near-ultraviolet spectra of emission nebulae (Fig. 5.2), active
galactic nuclei. and quasars are dominated by these lines.
Spectroscopic observations in the far UV began with the Copernicus satellite.
This was followed by the Voyager mission. which obtained low-resolution (AA 2
18 A) spectra of a small number of sources. Several short-duration experiments
on the Space Shuttle. including the Hopkins Ultraviolet Telescope (HUT) and the
Orbiting and Retrievable For and Extreme Ultraviolet Spectrometer (ORFEUS).
obtained limited observations. The Space Telescope Imaging Spectrograph (STt'S)
on the HST, which has an observational limit of ~1150 A. is complemented by the
Far- Ultraviolet Spectroscopic Explorer (FUSE). which is capable of high-resolution
(ll/A}. ~ 20.000) spectroscopic observations between 910 and 1130 A.
In addition to nebular emission lines. the resonance lines of many ions in the
diffuse ISM can be seen in absorption against UV continuum sources. Figure 5.3
shows a rich spectrum containing many interstellar lines. The most prominent are the
H Lyman series, including Lyy (972 A). Lyman a (949 A). H (s- 1) (937 A), and so
on. to H (14.1) (916 A).
In the FUSE spectral range. there are many resonance lines covering a range of
ionization potentials (e.g., 0 v1 11.1032, 1033 131. Si 111 All 103. 1113 A, Si tv M l 120-
1123. c "121977 A,ciu111175 i1,Nmi990 it, s III .11012, S w 11063. 1074 A.
S V! 10.933, 944, and P v M11113, 1 128) (Table 5.2). Figure 5.4 shows the ionization
stages of abundant elements that have observable resonance lines longward of the
Lyman limit. Beeause of bound— free absorption by He * in the photosphere. the flux
of photons emitted by normal stars shortward of 228 A is low. Three species (N‘H'.
85+. and 05+) have ioniaation potentials greater than this limit and are unlikely to
be photoionized by normal stars. For this reason. they are sometimes referred to as
"super-ions."
The ionization potentials for C”. N‘”. and 0“" are 47.9, 77.5, and 113.9
EV. respectively. These ions have lithium-like (ls22p —> 1:225) transitions in the
ultraviolet. namely. C N 2111548. 1550. N v 1111233. 1242. and 0 v1 11.11031, 1037.
If the C”. N“. and 0‘4 ions are produced by collisional ionization. then these lines
can be used to diagnose the presence of 1 x lip-K. 2 x IOj-K, and 3 it Ills-K gas.
Wavenumbcr Cm
tern") _ _ (eV)
Tnplcl Smglel
360000 I . «.44
l I
l I
l I
1 |
320,000 - I : — 39.50
| |
| |
I |
I |
230000 — l : — 34.57
I
|
|
|
240,000 '- | - 29.63
I
I
I
|
|
200,000 - I 24.69
|

160,000 — 19.75

I219

120.030 - 14.81

80.000 - 9.00

40.000 ~ d 4.94

0 I I
33 3}) Jpn JD IS 'P IPO 10

Figure 5.1
The energy diagram of C” showing some of I11: lowest energy levels of I11: singlet and triplet slams.
Pcrmirlcd lines are shown as solid lines. whereas lhc intercombinalion line from a triplet to a singlet
state (31” — 'S) is shown as a dashed line.
 5.1 Pennimdand Forbidden Transitions

Table 5-1
Examples of ultraviolet atomic lines demand by the IUE

“was”, (A) 10.. Tmnsilion (j — 1) Wavelength (A) Ion Transition (j — 1)

”15m, Cm 2p 3P”*2p2 3? 2423125 [Ne rv] 216345—2463 213
”39,43 Nv 2: 15- 2p 2!” 2410 [o n] 2,21 ‘5— 2p3 29
[30) Si u 3p2P°—3p“s 25H Hen paseneny
1335,35 cn 2p 21m 22:2 20 2663 Hel 2: 35— 1 lp 32°
:31: 0v 2p 'P°— 2p2 'D 2696 He! 2.: JS—9pJP"
Immg Si w 3: 25— 3p 2P” 2123 He! 2: 35— 3p 3P"
1391—1401 0 w] 2p 22°- 2p2 ‘9 2133 Hen then ,6
1433137 N 1v] 2:1 's— 2p 31’” 2163 He: 2: 33'— 1p 39°
1548150 cw 2.: 15- 2p 3!” 2134:2929 [Mg v} 2p“ 39- 2p‘ 1.9
.575 [Ne v} 21!;2 32'— 2p2 ‘5 2136 [Ar v} 3p? JP— 3p2 '3
.602 [Ne w] 2;:3 45°— 2p3 29° 27992803 Mg 11 1: 23— 3p 2 9°
[640 He u Balmera 219|r2191 Mg n 3p Zr—ad 20
I6ss-66 o m] 2P2 319—21::J 59° 2829 He : 2: 35—6,; 3!”
ma N :v 2p 'P"— 22;2 '0 283158 cu 2n2 15— 3p 1p“
1m Si u manta-5122'" 2931 Om 3]! 312—3113;”
“41.54 N m] 2p 113% 2.92 ‘P 2352 Mg 1 3:2 's— 3p 12°
1160 c [1 2p2 22)- 3p 1P0 2254166 [Ar w] 3;;2 ‘5— 3p2 29
ms [Ne m] 2nI 3? -- 2p4 '3 2929131 Mg 1| 3p 2130-4: 26'
1603111 55 n 3p 29°- 3p2 20 2929 [M3 v1 21:4 3p—2p4 '0
1662292 Si m] 38 15—3}! 3:” 2945 He! 23' 35—52132”
19mm c m] 2:2 15-2;; ’P’ 2913n9 NIH 3p 19—34 1190
2233 He n Paschcn 6 3023 om 33' 3.0"— 3p 3P
2291 cm 2p '2”. 2p2 10 3043141 o In 35 313°- 3,!) 39
23% He II Paschen 6 3063fll [N n] 2,02 3P— 2p2 lS
2321131 [0 m] 2p23P—2p1's 3I09I3005 [Arm] 3p“ 3P— 3p“ ’3
2325-29 c u] 2;! 19°- 2;;2 ‘p 3133 om 3p3s—3nr 3F”
2334-50 Si u] an 2923,11? 3133 He: 2; 35— 4p 3}”
1335 He II Paschen 6 3203 Hen Paschen a

Fm Kappa. 1.. and Allen L. H. 1981. in Sciennfie Aeeemptiehnem afrhe IUE. e6. Y. Kenna (ReidclzDordncht). p. 369.
 IN fi— 1— I j]; l I _I_ T l—I —' l —‘ I l— l l r l_l--

. V E I]
c In] -
F “I!“ “15"" mos .
- 11.0 t 0V l _
t O m] l j
_ Cw itum
1.1549 4
r ' ‘ l'i N m] C m C n]
'1‘: ' | 11151 12297 11325 olm '
a. 41.5 — ' r

E : [Ne NI ‘ l
En 1242.3 31 '
. F l Hen‘
I... - I l‘ l J
E --12.0 : Wt:

: I NEBCONT j

42.5 ~ —
_ STARCONT
4 4 1 4L . l l . l . . . u l . l
1500 2000 2500 3000
Wavelength (A)
Flgure 5.2
IUE spectrum of the planetary nebula NGC 7009 showing a number of recombination and
collisionally excited lines. For example. two lines of C III. the 122974 pennitted line and
M9084 intercombination lines in Figure 5. I, can be seen in this spectrum. The continuum is
due to a combination of stellar and nebular continuum radiation (from Harrington et' al. l98I.
MNMS, 195. ZIP).

P —I'—l I I _l— 1— _I'——l'_ —l_ —[—l

A : Kl-16(SiClB)
__'<2h Hell Clrv

E C
291--
”b -

E E
E“

Wavelength (A)

Figure 5.3
A large number of interstellar atomic (H I. O I. N I. Si n. P II. C III. and 5 v1) and H2 lines can be seen
in this FUSE specuum of the planetary nebula central star Kl-l6. The stellar lines (He II. C IV, 0 VI)
are marked above the spectrum (from Moos et aJ'. 2030. ApJ. 538. Ll).
 5.! Permitted and Forbidden Transitions 109

Table 5.2
aviolet
Examples of atomic lines in the far ultr
f .

1m Ti-ansition {j — 1) Wavelength (A) s,- 37- Au (5") f

Cu 2p 2,352.]: - 2p2 251;: 1037.0132 4 2 1525711109 1.2299: 10~I
2,, 21:32 _ 2132 ’51.»: 1036.3367 2 2 7.643314105 1.23071410"
cm 1,2 15° — 2p 11*: 977.020 1 3 1775051109 1.620514 ID"
Hm ”29;? 41922135,? 991.577 4 6 4.971110ll 1.10::10 '
.2
2P1p;_2_2p22DJ‘_ 991.511 4 4 3.1714107 1.201(10-2
2? 172,1, — 2,21 2173,; 939.799 2 4 4.13x10“ 1.211110 '
0 v1 2: 23.1,: — 2p 217,, 1037.6167 2 2 4.0‘1’1514108 6.53:10'1
2, 25.,2 — 2;} 2951.2 1031.9261 2 4 4.149x103 1.3251110—I
Si 13 3p 2pr — 5.123“; 1023.7002 4 2 2.131: 10‘ 1.68:: 10 -2
3p 219.91 — 5: 25.,2 10206939 2 2 1.0331103 115181-110—2
p .. 31.72319 - 45 JP” 11590365 5 3 5mm“ 6.201410 2
11569702 3 1 12:11:109 8.165410"
11550137 3 3 3.05xl0“ 6.101410 1
1153.9951 5 5 9.3lxl03 1.3153(10-1
11523130 1 3 4.l0x 108 2.431110-1
11499530 3 5 3.15410la 1.041.110-1
5 v1 3: 25....2 — 3p 29.1.2 944.523 2 2 1.61 )4 10° 2.15x10-1
3: 251:2 — 3p 11351,: 933.373 2 4 1.671: 10" 4.371: 10 '
For definition ofthe oscillator strength I. see Section 5.6.1‘Ible adapted from Morton. D.C. 2003.015. [49. 205.

respectively. The observations of these highly ionized atoms toward extragalactic

continuum sources can provide useful information on the distribution of hot (105-
106 K) gas in the galactic halo and intergalactic medium. Figure 5.5 shows the UV
absorption spectra of interstellar gas against the UV continuum of a Seyfert galaxy.
These results suggest that highly ionized gas is present away from the galactic plane.
At very high temperatures. heavy elements can be stripped of most of their
electrons. resulting in H-. He-. and Li-like ions. Because of the greater nuclear charge.
the inner electrons of heavy elements are tightly bound. Electronic transitions of the
inner electrons in highly ionized elements such as C“. N“. and 0“+ therefore occur
in the X-ray part of the electromagnetic spectrum. Figure 5.6 shows the spectrum
of 06"“ detected by the Chandra Observatory. The two inner electrons of 0°+ have
electronic configurations similar to that of He (Fig. 4.2), so emission lines from the
metastable state. for example. 233. can be used as density probes (Section 5.12). and
110 Line Radiation from Atoms and Ian:

MA)
150
I
0v

Pvt

Svu

er

CV

Siv
1 1 l J L I l
80 100 [20
at (8")
Figure 5.4
Ionization stages as a function of ionization potential for abundant elements (C. N. 0. Si. S. and P).
Stages with resonance lines in the UV and far UV observable by HST and FUSE are shaded. The
dashed vertical line indicates the ionization potential of He II of 54.4 eV. Ions to the right of this line
are likely to be ionized collisionally by high-temperature gas in the ISM (adapted from Massa er al.
2W3,Ap1. 586. 996).

the triplet shown can serve as plasma diagnostics in high-temperamre (10" K) and
density (it, ~ 103 — 10” c1114) regions. Several examples of X-ray lines from H-lilte
ions are given in Table 5.3.
Transitions that violate the L—S coupling selection rules can still occur via
electric-quadrupole or magnetic-dipole transitions. but their spontaneous emission
coefficients (A,1-. also referred to as the Einstein A coefficients. Secrion 5.5) are much
smaller than those of permitted electric-dipole transitions. ln terrestrial conditions.
the high frequency of collisions means that the upper state will be oollisionally de-
excited before it has a chance to self-decay. However. in interstellar conditions. the
time between collisions can be longer titan the lifetime of the upper state. allowing
the upper state to decay by entitling a forbidden-line photon.
Many of the strongest emission lines in the ISM are forbidden lines. Figure 5.7
shows some of the lowest energy states of the 0+ and 8+ ions under the p3 configura-
tion. All transitions shown in Figure 5.7 are forbidden because they involve transitions
within the same electronic configuration. and. therefore. violate the At = 5:15:15:-
tion rule. These lines are indicated by square brackets (e.g.. [0 11]).
The metastable nature of these states is indicated by their small spontaneous
transition rates. For example. the A3729 and 3926 transitions of [O [I] have A valufi
 40.0 I I I I l I I I 1—l I I I l I I Ifi 1 - I I I I I I I I I I I I I I-

Lya S 11 Si II :

30.0 _2

1
20.0

10.0 J_
0.0 .I l I I I I I I I I I I I I I I I I_ I I I I I I I I I_ l I I I I I I I I :

2.0

%
1|
L_
1,
i

0'01230
B'OFI I I—I I I I I I
124-0
1 I I I
1
I‘l—l'l I I l
1250
I I I—I—r I I I I—rI
1260
. . I . I-

— SiIv SiIv :

5‘60:— l r . l- 0 TI_
2“ I: ' 'i =‘ ‘ _ j. ‘ :
1- : I

U : ..

.520:— 5
'
9”on.......I_.I.I,....I.LI..II_LII......I.‘:
EIDT :I

13:90 1400 I410

9'”
O

.I

—I
E!‘

.I

4
TTrfi‘Y‘rT‘n—fi—F

II'IIII1|||I|I1l|
E

C054? C rv CN
F"
O
P
O

.
.
.

0.0 L J. I I I 1 I .I _I I I I I _ L _I_ I. I I I I I I l I I I I
2.0 L _
0.0 4 ‘
[520 1530 1540 1550
Wavelenglh (A)

Finns:
"57 GHRS Spam showing N v. Si w. and c IV and other interstellar absorption lines mm Ihc
SM“! 1 galaxy 550 141-055. The only other Line present is the mdshifiul Lyman a (z = 0.003492)
(adapted from Scmbmh a at. 1999. ApJ. 524. 90).
 2CD- Capella 0 vu triplet
LETG I order
Counts

Wavelength (A)

Figure 5.6
Chandra Low Energy Tram-mission Grating (L570) spectrum of the star Capella showing the O VII
2' P — 1's resonance line(labelled r). 23? — I'Sintereombination line (labelledr').and M233 — 1's
forbidden line (labelled f). See the energy diagram of He for reference (Fig. 4.2). This triplet of lines
is seen in many hot stars. (From Brinkman «01.2000. ApJ. 53-0, L] I l.)

Table 5.3
H-like ion lined in the X-ray region

Ion Transition A (A)

Fe XXVI Lyn 1.18

8 1m Lyn 4.12
Si mv Lyfi 5.21
Lyn 6.17
Mg rm Lyy 6.73
Lyn 8.40
Ne Jr LyS 9.43
Lyn 12.11
N vn Lyn 24.78
 5.2 Transitions within Multiple“ 113

2“’17:
2pm

1pm

7331 7320 73317 7319 2

“P11? I

10336 102137
1931:
2470 2470 10371 1c321
z1'.)5!: ‘ 1 ZD

so

J 4076 4069
Inn 1
3729 3726
6731 6716

431,: r l' 1 45M , 1r if V

8+
0+

Flgure 5.7
Exampls of forbidden transitions within the ground-state multiplet of the ions 0+ and 8*:
both are in the p3 electron configuration. Fach transition is labelled with its wavelength in A.

of 3.6 x 10'5 and 1.8 x [0" s". respectively. The corresponding lifetimes of the
upper states 205/2 and 203,; are 7.7 and 1.5 hours. respectively.

5.2 Transitions within Multiplets

For atoms in good L45 coupling. the relative strengths of the transitions within a
multiplet obey the following sum rules:

0 The sum of the strengths of all lines of a multiple: that end on a cominon final
level is proportional to weight ZJ’ + l for the final level.
0 The sum of the strengths of all lines of a multiplet that Start from a common initial
level is proportional to the weight 2.! + l for the initial level.

Let us consider the 4 P —“P multiplet. an example of a symmetrical multiplet. Since

S = 3/2 and L = l. the possible values for J are 112. 3/2. and SIZ. Among the possible
9 combinations. the transitions between I = In and J = 5/2 are not allowed because
of the A] = 0 or 1 selection rule.
114 Line Radiation finnl Atoms and lens

Table 5.4
Relative strengths of the multiplet ‘P -—‘P
‘P
J\J 5/2 312 1’2

5’2 It )4; 0
3’2 JV: ‘2
4P 1/2 0 y; :3
50 12.6 5.40 0
312 5.40 1.60 5.00
112 0 5.00 111)

Usually the strongest line in the multiplet is the line involving the largest J
value (II in the example in Table 5.4). The values of relative transition strengths
can be looked up in tables (e.g., in CW. Allen 1973. Astrophysical Quantities. 3rd
edition, section 27). In the PP table under the column (25' + 001.. + l)(2L2 + I) ~_-
(4)(3)(3) = 36. we find 1' = 12.6. :2 = [.60. 13 = 1.00. y] = 5.40. y; = 5.00. By
summing up the relative strengths by rows or columns. we find ratios of 18:12:15 =
3:2: I. which are proportional to the statistical weights 2] + l = 6, 4. 2. giving ratios
of also 3:2: 1.
As an example of a normal multiplet. defined as multiplets involving L —+ L + I
(cg, 5 —» P or P —> D). we consider the multiplet ‘P —‘D. Under the column
of (ZS + l)(2LI + ”(21.2 + l) = (4)(3)(5) = 60, we find the values for the relative
strengths in Table 5.5.
Summing up the values of each row, we have ratios of 30:20:10. which are pro-
portional to weights of {26/2} + l] : [2(3/2) + l] : [2(l/2) + l] =6:4:2. Summing
up the columns, we have ratios of 24: 18: 12:6, which are proportional to the statistical
weight ratios of 826:4:2.

Thble 5.5
Relative strengths of the multiplet ‘ P -‘D

‘0
JV “”2 5f). 3;: m

512 I] _)'] 2| 0

3,2 0 I; y; 22
JP “'2 0 0 1'3 )3

512 24.00 5.40 0.60 0

312 0 I160 6.40 LOO
NZ 0 0 5.0) 51])
 5.3 Fine-Structure Lines 115

5.3 Finesuucture Lines

Transitions between levels in the same term (same L and S) but different J are
known as fine-structure lines. In the first approximation. the fine-structure levels are
split as a result of spin—orbit interactions (Fig. 4.3). For example, in a p2 electron
configuration. the 3? state is split into J = L + s = o. I. or 2. resulting in the
390. 1.2 levels (Section 4.2). The 3?” ten-n ol‘ He l (ls2p, Fig. 4.2) has two fine-
structure transitions. 3P; — 3Pf at 29.616 MHz. and 3P1" — 3P; at 2291 MHz. A
precise experimental measurement of these transitions allows the test of contribution
to the fine suucture beyond spin-orbit interaction. including small contributions due
to quantum electrodynamic corrections.
The ground state of neutral carbon (C t), with an electronic configuration of
Is2 2:1 2p2, has fine-structure lines at 3P, - 3P. (370 um) and 3P. - 3P0 (609 um).
Doubly ionized 0 ([0 ml), with the same 2p2 configuration, has similar transitions
at 3P2 — 3P1 (52 pm) and 3P, — 3P0 (38 am). In addition to C 1, other neutral atoms
such as 0 I can also be detected via their fine-structure lines. Due to the small energy
separations. these lines generally lie in the infrared. Examples are 3P. - 3P2 (63 Inm)
and 3P0 — 3?. (I45 Irim) lines of 0 t (Fig. 5.3), and the 3P2 - 3P. (l22 um) and
3P. - 3P0 (205 ,um) lines of N II. The 63-um line of O t was first detected in M17
and M42 with a 30-cm telescope on the NASA Lear Jet in l979.
Because these lines arise within the same multiplet, they are forbidden transitions.
Although the C r 609-um line is a magnetic-dipole transition. the high Mooney;
of this transition and the v3 dependence of the Einstein A coefficient results in the
609-um line having an A value (7.9 x l0‘95") that is about the same as that of
the pen-nitted CO J' = l - 0 A2.6-mm rotational transition. Because of their different
required excitation conditions, the strength ratio of the two ground-state fine-structure
lines is a sensitive tracer of the total gas pressure. The C I 609-um line was first
detected with the 0.9-m telescope on the Kuiper Airborne Observatory, but is now
routinely observed with gmund-based telescopes. Figure 5.9 shows the C l line in
NGC 7538.
Because far-infrared lines are not afiected by dust extinction (Chapter ID), the
fine-structtue lines of C are useful in tracing the structure of the Galaxy. Atomic
C has been found in both diffuse clouds and molecular clouds. The [C t] emission
from the inner 3 degrees of the galactic center region was mapped by the l.7-m
Antarcric Submillimerer Telescope and Remore Observatory (AST/RO) located at 2347
m altitude in the South Pole in 200l-2002. Both the 370- and 609-ptm lines are seen
by CORE throughout the Milky Way. and they represent a significant conu-ibution to
cooling of interstellar gas (Table 5.6).
Another example of fine-structure lines in the far-infrared and submillimeter
wavelengths is the sz — 2P”; line of C ll at 158 ,um. Since the ionization potential
of C is lower than that of H (l LZS vs. l3.6 eV). photons with wavelengths between
llOl.72 A and the Lyman limit are not absorbed by H and are available for the
ionization of C. In comparison. the ionization potential of N is 14.5 eV, so N is
expected to be neuu-al in H l clouds but ionized in H n regions. In clouds exposed
to UV. C is mostly in the form of C+ to a depth of visual extinction AV =l—5
(Section I02).
116 Line Radiationfrom Atom: and lens

[01163,um
. . . . I t . . v I . . 3 I'IIIIIIIIIII

Illlllll
IIllIlIJIIIII
NGC1333—IRASZ IRAS 03282

”11
62 63 64 62 63 64

:30»...,...:,..6o_...,....r1. 30:”..[flnj _
5 LlSTI—MM : : ; usamm 5
6E 40 _— 1 20 .— ':
u ' : E E
E 20 _- -_ l0 .— 1
:5 : : : E
E 0 0 " l I I 1—] I I I

62 63 64 62 63 64 62 63 64

60 I I I l l I I I I I I Ij- 6 I l I I I I I 1 I I l l 30 I l I l ' l' I I I I 'I—I:

_ ms 13273 : L723—MM Ll l57—MM 1

4° .- 1 2o 1
20:- -: 10 -:
o' ' o '
62 63 64 62 63 64 62 63 64
101m)

Figure 5.8
The 63-um fine-strucrure line of [0 t] has been detected in a number of protesters by ISO L‘WS
(Giannini et al. 2001. ApJ. 555, 40).

Because of the low ionization potential of C. C+ is widely present in the ISM.

The [SB-um line was first detected in NGC 2024 and M42 with a 30-cm telescopeon
the NASA Lear Jet in I980. Figure 5.10 shows the galactic map of the 158-um line of
C n. The COBE measurements estimate total luminosity emitted by dust in the Milky
Way Galaxy to be (1.3 :i: 0.6)(R0/85 kpc)1 x 1010 L9 within the solar circle (no). In
comparison. the total luminosity in the C It line is approximately 5 x 107 Lo (Table
5.6). or about 0.3% of the dust luminosity. Observations of the C II line in external
galaxies show that it is often the single brightest emission line in the spectrum of
galaxies and luminosity of the line can be as high as 1% of the dust luminosity (SEC
Fig. 17.6). Galaxies with strongest C [I line strengths are often gas-rich galaxies with
strong star formation activity. Since infrared lines are less afiected by dust extinction
 5.3 Fine-Stratum Lines 117

6_o-—1'1'1'1
NGC 7538 11181

l _1_ _l 4— J_
-l40 —|20 —100 —80 —60 —40 —20 0 20
V(kmls)

Figure 5.9
A spectrum of Ihe 609-um (490-GH2) C I line Iaken at the James Clerk Mme" Telescope.

Table 5.6
Total luminosities of the Galaxy emitted in various
infrared cooling ling as measured by COBE HMS

A log L
Species Transilion (um) (L9,)

co J=2¥ 1 1302 4.9

co J=3 -2 867.2 5.1
CO I _4- 3 650.4 4.1
CI 3P, - 3P0 609.1 5.3
CO I = 5 -- 4 519.11 5.0
C1 3?; — 3?. 370.4 5.5
N11 3p, In, 205.3 6.7
Cu 2PM — 2PM 157.7 7.7
Nn 1P, — ’9. 121.9 6.9
Adapted from Wright el' al. I991. ApJ. 381. 200.
118 Line Radimr'on from Atoms and Ions

Figure 5.10
A grey-scale map of the galactic emission of the ISS—um C II line as observed by the CORE Far
lnfraredAbsolute SpectmphomrerfFlRAS). The map is plotted in Aitoff projection with the galactic
center (8 = 0 at the center and C = :hlBO" at left and right edges). The galactic poles b = 1:90" are
at the top and bottom. The grey scale represenls the integrated intensity 0! the line emission at 7°
angular resolution. The black regions are areas not covered by the survey.

than Optical lines. C u is a better tracer of star formation than Hat. With next-generation
instrumean such as Herschel and ALMA. it will be possible to observe the C 11 line
for a large number of galaxies at different redshifts and therefore determine the star
formation rate as a function of the age of the Universe.
Many fine-structure lines have been detected by the Infrared Space Observatory
(ISO) (see Table 5.7 and Fig. 5.11). Since laboratory measurements of highly ionized
species are difficult the most accurate rest wavelengths of many of the fine-structure
lines are obtained from space astronomical observations. By using lines with well-
known wavelengths (such as the recombination lines of H and He) as a reference.
the wavelengths of infrared fine-structure lines can be derived from high-resolution
spectra of emission nebulae. From data obtained under the ISO SWSO6 gratings
(MA). ~ WOO-2000) or Fabry—Perot (l/AJ. ~ 30.000) modes. wavelength accuracy
up to one in 105 is possible. Some of these improved measurements are included in
Table 5.7.
Some s-process elements. such as K: (Z = 36) and Sc (2 = 34). have fine-
structure lines in the near infrared. The ground-state electronic configuration of Kr++
is 4P4. which is similar to the energy structure of 0 i. For example. the 2.199-
um 3?. — 3P2 transition of Kr In is equivalent to the 63-um transition of 0 t. St:3+
has a ground-state electronic configuration of 4p and its 2P3}; — 2P”; fine-strum“?
transition has been suggested as the source of the long-unidentified infrared emission
lines at 2.23? pm (Fig. 5.12).
 5.3 fine-Stratum Line: 119

Tabla 5.7
Awmic and ionic fine-structure lines in the infrared

Transition Wavalengm Transition Wavelength

Inn 0' - 1') (um) Ian (1‘ - 7') (34m)
[31 v11] 319. 7- 3P; 2.433 [141 v] 3P. — 19:, 13.102
[Si 11:] 3P1 - 3P. 2.534 [Mg v[ 3P0 - 3m 13.521
[AI v] 29172 — 2PM 2.905 [No v] 3P; — 3a 14.322
[Mg v11'11 2pm — 11°,,2 3.023 [Na w] 319. — 37-0 14.395
[K1711] 233,-, — 119.” 3.191 [N43 111] 11D. — 313, 15.555
[Ca IV] 219”; 9 133,; 3.207 [Sm] 332 -- JP. 13.713
[A] v1] 3?. — 3P; 3.550 [Cl [V] 3P. — 33., 20.311
[C3 1711] 3F; — 3P] 4.035 [Ar n1] 3P0 — 3?. 21.330
[Ca v] 3P. - 3P; 4.159 [Ne 91 319,- 330 24.313
[Mg IV] 119.” — 2173,, 4.437 [01v] 1pm — IP32 25.390
[Ar 93 1pm — 13,” 4.530 [Fe m] ’172 —5 173 33.033
[14 m] 219.,2 — 23°37: 4.513 [s m] 3.0, — 3.00 33.431
[N3 wu 23m — 1P”; 4.535 [31111 233,», -- 11in...2 34.315
[Mg vu] J192 — 3P. 5.503 [Ne m] 330 - 3?; 36.014
[Mg v] 3P. — 3P, 5.510 [F [V] 3191— 33., 44.070
[14 w] 3m — 37>: 5.932 [Fe 111] ’01 —5 172 51.530
[31 VII] J19D — 3P1 5.492 [0111] ’192 — 1m 51.314
[C19] 19372 — 2P”; 5.707 [31] 3P0 -- 33. 55.311
[Ar 11] 2191,2 — 2103,, 5.935 [N111] I’m — 2pm 57.317
[N3 111] 2P0: — 1193,, 7.313 [P11] ’15 — 3P0 50.540
[Ne v1] 23m — 219”, 7.552 [01] 319. - 3P2 53.134
[Fe v11] 1F; — 3::3 7.315 11:11] 33,, — JP. 57.200
114: v} JP, — 3?, 7.902 [511] 3P1 - 1P. 53.473
[N3 111] 3192 - 3P. 3.511 [0 m] 3P. — 33., 33.355
[4: 111] 3P. — 3P2 3.991 [A1 11 1P3: — 119m 39.237
[N3 IV] 319, — 3P; 9.041 [F3111] 5170 J 0. 105.370
[Fe v11] 3F, - 31"; 9.527 [N 11] 3P2 — 319. 121.393
[3 1v] 293,2 — 1Hum 10.510 [311] 3P. -— 319.J 129.532
[Ca V] 3190 7 3P, 11.432 [01] 3P0 -3P1 145.575
[Cl IV] 3192 — 3P1 11.752 [C 111 sz — IP17: 157.741
[Ni ul ‘an -‘ Fm 12.729 [N u[ 3P. — 3P0 205.173
[Nan] Hun—13m 12.314
 I l' I I i i i I I

i «3%
10000 ? GC Ssr A“ E
_ SW30] E.
F
E IOU) 5-
b
'2 :E

3n - EIn
E IOO E- “

i
to :—
I l l | | l _1 I i J. |

3 5 10 20 40
Wavelength [pm]

Figure 5.11
ISO Short Wavelength Spectrometer (SW5) spectrum of the galactic center showing a number of
infrared fine-su'uclure lines. The continuum is due to dust emission. The broad absorption features at
I0 and 13 um are due to amorphous silicates (see Section ll.2.I) (from Lutz et al. 1996. AM. 315.
L269).

Kr Ill 4p‘ Se tv 4p

5424A

6828 A

I g I 13.1 pm 2PM
2.199 m ' 2.237 m
:_!__._L “ m__r___ ”
Figure 5.12
The two infrared lines at 2.199 and 2.287 um were unidentified for 25 years. With high-
resolutioo infrared spectroscopy, they an: identified as fine-structure lines of s-procws elements
10'” and Se” (adapted from Dinerstein 2031. ApJ, 550. L223).
 5.3 Fine-Structure lines 121

fir l I ‘i l '7 I

[Zn IV] 3.625 pm

3 — _

15 l'

:x

E 2- *
E“
79 l
a NGC7027

:
l: l _ _
l l
H120—6 Htl9—6

l I I
[C 5|]?

0 . . L l . . . . 1 . . . . l . . i . | . . .

3.60 3.61 3.62 3.63 3.64 3.65

Heliooentric wavelength (vac. pm)

Figure 5.13
UKIRT C634 spectra of two planetary nebulae showing the detection of the 3.625-um fine-
structure line of [Zn Iv]. This collisionallyr excited line is stronger than the recombination lines
of H. two of which can be seen in the same specu'um (adapted from Dinerstein and Geballe.
2001.14,”. 562. 515).

The high efficiency of collisional excitation makes possible the detection of

forbidden lines of ions of very low abundance. Figure 5.13 shows the detection of
the 3.625-um line ofthe 203,1 Jom fine-structtue transition of 2n+3 (35231963119).
Both Se and K: have solar system abundances of approximately a few times 10 9.
and the solar system abundance of Zn is estimated to be 5 x 10'5.
122 Line Radiation from Atom and Ian:

5.4 Hyperfine Lines

Line splittings due to the effects of nuclear spins (I) are called hyperfine lines. The
total angular momentum vector can be defined as the vector sum of L + S + l, and the
quantum number F can take on values from the smallest positive integer or half integer
that can be formed from L , .S'. and l . up to L + S + I . The selection mics for electric.
dipole or magnetic-dipole transitions between hyperfine states are A F = 0. it. With
F = 0 -—+ 0 forbidden.

5.4.1 21-crn H Line

The H atom has a nuclear spin of 1/2, and hyperfine structure doubles all energy levels,
In the ground state of H (113,”). there are two hyperfine states: F = J + I .-= 0 and
I. The transition between these two states has a frequency of 1420 MHz (121cm),
which is widely detected in the ISM.
Although the 22 3m and 21?“; states of H are predicted to have the same energy
by Dirac‘s relativistic model of H. these two states in fact are observed to have
a splitting of l057.9 MHz. known as the Lamb shift (Fig. 5.14). This splitting is
explained by the theory of quantum electrodynarnics.

Dirac Quantum Hyperfine

theory elecuodynamics splitting

1 / —--—-—--—- F= 2 --
,1 = 2 _.—-pm------ _1P3,2 <‘ F I 23.7 MHz
\ ..___._____ = l _.

10369JMH7. . F=l—' _._.

I
I
i 25m<\ [77.56 MHz
t' \. _____._______.___ _ —_ —u—
n = 2 ——‘Pm— 15m: 1057.9 MHz F-°
‘ I —-——-—F= ] —- ——
‘- 1P,,2<: 59.19 MHz
‘ F = O - - ---—

Lyman aat [215.67 A

I ———F=l --
[I

,-- —-- is.“ l 420 405 751.7112

n = I ——'ZS”2" 3.6 GHz \\ F 0

Flgure 5.14
The hyperfine strucnire of the lower states of the H atom (adapted from Bernath I995. Spectra of
Atom and Molecules, Fig. 5.] B).
 5.4 Hyperfine Lines I23

The ground state (ls) of hydrogen can be in one of the two hyperfine states de-
pending on whether the spins of the electron and proton are parallel (F = I + S = I) or
antiparallel (F = 0). Since both the upper and lower states have 8 = 0.e1ectric-dipole
transitions are not allowed. The low magnetic-dipole transition probability together
with the low frequency of the transition (v = 1420.406 MHz or Jt = 21cm) results
in a very small spontaneous transition rate of 2.869 x 10‘15 s‘l (corresponding to
f = 5.75 x IO‘”; see Section 5.6), or 23 orders of magnitude weaker than the Lya
line (Section 5.1 I).
Similar hyperfine splitting also occurs in the excited states of H. For example.
the F = l — o hyperfine transitions onSW and 1P”2 states are at 177.56 and 59.19
MHz. respectively (Fig. 5.14).
For elements heavier than H. the total nuclear spin depends on the sum of the
total nuclear spins of the nucleons (protons and neutrons in the nucleus). Although
I is often called the nuclear spin. it actually refers to the total angular momentum
of a nucleus and not just the spin alone. The nuclear shell model suggests that
nucleons of the same kind tend to combine with one another to yield zero angular
momentum. therefore all even—even nuclei are expected to have I = 0. Consequently.
a nucleus with an odd number of nucleons is expected to have spin of the odd
nucleon. For example. the six protons and six neutrons in '3C are paired up as an
even—even core. and the ground state of the entire nucleus (1 = 1/2) corresponds
to the angular momentum of the remaining lone neutron. For odd-odd nuclei. their
total angular momentum is the combination of the angular momenta of the two odd
nucleons. A list of the nuclear spins of common nuclei is given in Table A2.2 The
hyperfine transition (F: 4 —> 3)In the ground state (6s 23”,) of Wes (1: 7/2)
has a frequency of 9192.631770 GHz andis used as a frequency standard'in atomic
clocks.
After the H )tZl—cm line. the next atomic hyperfine transition detected in emission
from the [SM is the Isa—hm 2pm — 1P”. F = 2 — 1 line of ['3c u]. Recent high-
resolution near-infrared spectroscopy has allowed the detection of 3P. —3P2 hyperfine
transitions of [Na Iv] (9.0 pm) and [AI vr] (3.66 pm). Since 27Al and 2‘’Al have
nuclear spins of 512 and 5. respectively. they have difierent hyperfine structures.
The nondetection of the expected hyperfine components of 2“AI allows One to set
a stringent upper limit of 1/33 for the isotopic abundance ratio 26ANNA]. This is
particularly significant because 16A] has a very short half-life of 7.2 x 105 yr. and its
existence (e.g.. in meteorites) is evidence of recent nucleosynthesis (Section 15.9).

5.4.2 lntercombination Lines from Hyperfine States

The 3P"— '5' multiplet ofC++ hastwo intercombination lines. the 3P"— lSOelectric-
dipole transition at A 1908.7 A (A: 104 s" ') and the 3P"— '30 magnetic-quadrupole
transition at 11906.7 A (A— - 5.19 x 10'3 s") (Figs 2.5 1 and 5. I5). Similar pairs
of transition are also present in other beryllium--1ike (2s2p) ions. such as N tv
1148311486 and Si Ill 1188211892 (Table 5.1). Because of the large difference in
transition probabilities of these pairs of lines. their ratio is sensitive to collisional
excitation. and therefore can be used as density probes (SectiOn 5. I22).
124 Line Radiarl’orl from Aroms and Ions

lzcla l3c2+

J F

._._ 2 5’2
an

3 3’2 J
P: I in FF:

0 m

1907 1909 I9")

is. o in ms
Figure 5.15
The 3P0 -'S multiplet of C“ for '2C and 13C. The energy separations are not to scale. The
numbers next to the transitions are wavelengths in units of angstroms (adapted from Clegg er
al. 1997, MNMS. 234. 348).

The third transition of C III. 3P; — 'so at A 1909.6 A. is stn'ctiy forbidden (Sec-
tion 5.1). However, if the carbon atom has a finite nuclear spin (as in 13C where
I = U2). the multiplet is further split into hyperfine states (Fig. 5.15), and the
3P3 — '30 F = 1/2 -> 1/2 transition is possible. This line was first detected With
the HST Goddard High Resolution Spectrograph.
This electric-dipole transition is expected to shift slightly in wavelength due to
isotopic effect and is found to have a wavelength of 909.59? A. 'ntc simultaneous
measurements of the 3Pl" — 'SD and 3P2“ -— '50 lines of ”CH and the 3P6 — '50 line
of ”CH in the same spectrum allow adirect estimate ofthe I2c to I3t: isotopic ratio.
and therefore can serve as probes of nucleosynthesis.
Another example of the nuclear-spin-induced transition is N Iv. Both stable
isotopes of N, l"N and l5N. have nonzero nuclear spins (I = l for I‘N. and I = 1/2
for 15N). This allows the 3P; —- '50 line at 1437.39 A to occur. This line has been
 5.5 Absorption and Emission 125

observed in the planetary nebula NGC3918 with the HST Space Telescope Imaging
Spectrograph (ST[5). Since this line has one of the slowest observed transition rates
(4 x 10 4 s", with a corresponding lifetime of 2500 s for the 3P; state). it is
impossible to study in the laboratory because of collisional de-excitation. Low-density
astrophysical plasmas with large enough size to provide adequate emission measures
are the only laboratories to study these hyperfine transitions.

5.5 Absorption and Emission

There are three radiative processes that can take an electron from one state to another
in an atom. It can undergo a spontaneous decay from a higher state i to a lower
state j accompanied by the emission of a photon with energy h v equal to the energy
separation Eu between the two states. In general, the photon is emitted over a finite
fiequency interval dv with a normalized line profile tlrv. where 1:: limit: = l. While
the shape of Wu depends on the broadening mechanism (Section 5.3). spontaneous
emission is isotropic and can be considered to be independent of angle. Over short
time intervals At. we can define a transition probability A” such that the change in
the number density of the upper state (Ani) is given by —n,-AU- At over all solid angles
and all frequencies. This coefficient AU is called the Einstein spontaneous emission
coefi'icient and has the unit of inverse time.
A second way for an electronic transition to occur is through the absorption of a
photou with energy hvij. causing the electron to go from j to i. Since the transition
rate is dependent on the local radiation density. we can define the coefficient 31,-.
called the Einstein induced absorption coeflicient. in terms of the number of photons
absorbed per unit volume in time interval At,

An,- = Maj-Jet, (5.1)

where

i=1 d—w f 1..»qu (5.2)

4n

and o” is the normalized profile of the absorption (fan ¢udv = l).

A third process where the same background radiation field can cause a downward
transition was postulated by Einstein. This process is analogous to the forced oscil-
lation of an electron driven by an external electric field (Section 5.6) and is known as
stimulated emission. The Einstein stimulated emission coefficient BU‘ is defined the
same way as Bji:

An,- = —n,-B,-j—J7At. (5.3)

Usually. stimulated emission has the same angular dependence as the incident radia-
tion (1,.
126 Line Radtiatianfiom Atoms and fans

According to the principle of detailed balanceI where these internal M8

result in no net change in the level populations or the radiation field. we have

(na'AJj+nlBij‘i)=nijij' (54)

Under thermodynamic equilibrium, IL. is given by the Planck function (eq. 2.36):

Mfi 1
l(u = Bu = c2 gnu/tr _ l‘ (5.5)

Since 3., changes only slightly over the line width.

_ CD

12%] mn=sw on
0

Also. the population distribution is given by the Boltzmann equation.

"i = fle—nu/tr
(5.7)
i 31'
where g,- and gJ- are the degrees of degeneracy in the upper and lower states. respec-
tively. Substituting eqs. 5.5. 5.6. and 5.7 into eq. 5.4. we have the following identities:

3; an =
__._. 1, (5.8)
8i B.“

At; 2M3
—— = . 5.9
B,“ C2 ( )

Since the Einstein A and B coeflicients are fundamental properties of the atom
and are not dependent on the environmental conditions, these identities are true even
if the atom is not in thermodynamic equilibrium.
The effect of line absorption is to remove energy In: from the background
radiation at a specific frequency over a frequency range of dv according to the
distribution 451,. Since the background radiation causes both absorption and stimulated
emission. the net energy removed is the difi'erence of these two processes. Using the
definitions of absorption coefficient (eq. 2.63) and Einstein B coefficients (eqs. 5.!
and 5.3), we can write the absorption coefficient far a b—b transition as

hv
“u = III—("jflji'ibu - "iBrj'l’ul (5-10)

The second term is due to stimulated emission. which can be considered as negative
absorption. The units ofx” aiecm2 cm"3 3" 112*. Similarly. the emission coeflicient
is given by

_ hu
J'v = Eni‘qlfll’v- (5'11)
 5.6 Spectra! Line Formation 127

In the ISM. the emission and absorption profiles are dominated by Doppler effects
(Section 5.8) and generally can be considered to be equal (111” = ¢v)_ In this case. the
source function 5,, = jv/x, is

v:
Aij/Bij {5.12)
£1311 _ 1.
"int;

Substituting eqs. 5.8 and 5.9 into eq. 5.12, the source function can be expressed as

2hch2
3,, = ET (5.13)
MM

In the case of b—b transitions. we are dealing with atoms or molecules instead
of bulk matter. It is sometimes more convenient to use an absorption coefficient per
atom rather than per volume. We can define the atomic absorption coeficienr 0., by
K
a” = —”. (5.14)
"J.

ah has units of cm2 and has the physical meaning of a cross sectiou. Comparing this
equation with eq. 5.10 and making use of eq. 5.8. we have

a” __. (. _ $.51) ’“’ 31.11;... (5.15)

"j 3i

Under LTE conditions. the population ratio is given by the Boltzmann equation, and
eq. 5.15 becomes

a” = (I e hwlT) fiaji¢0'
(5.16)

The term in parenthesis is sometimes referred to as the correction term for stimulated
emission.

5.6 Spectral Line Formation

All bound states of atoms and molecules have finite lifetimes (At). From the uncer-
tainty principle, the energies of bound states are subject to uncertainties given by
MAE ~ 71 and the spectral lines formed by bound-bound (b—b) transitions in ab-
sorption or emission therefore have finite line widths. We can define a normalized
line profile ¢v (where f dvdv = 1) to designate the shape of the spectral line.
The theory of line formation was first developed using the classical model where
the atom is approximated by a harmonic oscillator. An electron is attached to the
nucleus by a spring and undergoes harmonic motion. Radiation as a result of the
128 Line Radiation from Atoms and [arts

acceleration of the electron simulates the effect of spontaneous emission. Such mm

tive losses can be regarded as a "frictional" term in the equation of motion. The fact
that the spring has a natural frequency that can respond to external radiation to Cause
resonance can be used to approximate the process of line absorption.
The motion of an electron attached to a spring is given by

mi = —-m,wfiz — maxi, (in)

where mo is the natural angular oscillation frequency of the spring and y is the
damping constant due to radiative loss by an accelerating electron. In the case of
underdarnping (y < 2‘00), the solution of eq. 5.17 is

2(1) = zoe'iy' cos wot. (113)

Since the total energy of the oscillator is given by

1
wm = Emcmngm. (5.19)

where 2m = zoe'iy'. substitution of eq. 5. l8 into eq. 5.19 shows that thetotal energy
of the oscillator decreases exponentially with time:

we) = W(D)e"”, (5.20)

where W(O) = émpfizfi. The formula for radiative loss by an accelerating charge is

E = ,‘292 (22)
ch 35 (5'2”
where () denotes the average over one period. and for a harmonic oscillator it is given

(2'2) = [I,1m“ zimwg cosz(wut) dz] / (a)

[Ii-«“3 (%)l We?)

l 2 (as. (5.22)
52"“:
Substituting cq. 5.22 into eq. 5.21. we have

dw 2033
we). (523)
dr 3mg:3
 5.6 Spectral Line Fomrau'on 129

which. upon integration, gives

3.2
w = wrap—till. (5.24)

Comparing eq. 5.24 with eq. 5.20. we have an expression for the damping
constant

'2 2
= 36—”!
3 met:3
(5.25)
Since II)! is the lifetime of the electron before it decays as a result of self-radiation, the
damping constant can be viewed as the classical analog of the spontaneous emission
coefficient A.
In this classical model, an atom in a radiation field can be approximated by
a harmonic oscillator with natural frequency coo in an oscillating elecu-ic field of
frequency 0). Assuming that the solution to the equation of motion

me}: = —m,yé — mpgz + eEe“m (5.26)

has the form 2 = 203“”, we can find a particular solution to eq. 5.26:

—wzz = —i-ymz — £952 + iEoe‘l‘” (5.27)

me

E in»
z = iT—°§—___. (5.28)
to, too — to + rye)

The displacement of the electron is at maximum when m =aro. This resonance is

analogous to the b—b uansition of an atom. Each of these displaced electrons will
induce a dipole moment p = 22. and if there are N oscillators per unit volume. the
electric displacement created by the dipoles is 41: N92, so the total electric field in the
medium is E + 4JrNez. and the dielectric constant E is given by

41rNez
E=l+

2
=1+4rrNe— I
m, coo —- a) + two

The index of refraction, ’N, is defined as the ratio of the speed of light in a vacuum
to its speed in a medium. Since the velocity of light is also given by c/JE, N = J?
and can be a complex number with real and imaginary parts. The complex index of
refraction is written as n -— it: where n and k are referred to as optical constants. For
130 Line Radiation from Atom and lens

gases. the second term in eq. 5.29 is small and the square root of 6 can be ohm,“
using the binomial theorem:

n — Ht = E ”2

z I + (ZINe 1 ) 2 l _
me too — all + tyw

= 1 + 2nNez) ”3“”2—iyw
. .
( m, ((wfi — at!)2 + rsz (5 3°)
Separating the real and imaginary parts of eq. 5.30. we have the optical constants:

l+(2nNe2) “3"“?
n = —— 53
me '
((03 — ‘92}: + V2“): ( ”
k = ( 23ml)
mt __. rw
((0% _ (1)2)2 + Yzwz (s. 32)

The change in the electric field passing through the medium is E = Eoeiwi“5)
where the group velocity v is 75;. Since the radiation intensity is proportional to
EE", the attenuation of Ihe intensity is dependent only on the imaginary part of the
optical constant:

I: toe—Er”. (5.33)
For this reason. it is sometimes referred to as the absorption index whereasn is referred
to as the refractive index.
In a constant density medium. the intensity decreases exponentially with optical
depth, 1 = lac-W. Comparing with eq. 5.33 and making use of eq. 5.32. we have
”(to
xv = ——
c
411’ N62 ya):
(5.34)
nice (to: — a?)2 + yzwzl
We can see that the absorption coefficient peaks sharply and is nonzero only
when a) 2 (no. Therefore, to}, — :92 can be approximated by (con — w)(wo + w) 2
(mo — mflw and eq. 5.34 can be rewritten as

477N£2 ywz
= 5.35)
" mg: (too — (4,024.11:2 + yzwz (
2 2
= N (11) J&_' (536)
mac (5102 + (14417)2
where Av = (we. - cu)/2.1r. Equation 5.36 is lcnown as the Lorentz profile.
 5.6 Spectral Line Fortttation 131

The atomic absorption coefficient (a..) is defined by it" = Na, (eq. 5.14). Since
K” has units of cm"' (Section 2.6). a, therefore has units of emz, or cm? 5—! Hz-I.
The total atomic absorption coeficienr is defined as

a =f avdv. (5.37)
D

and has units of cm2 s- '. Substituting eq. 5.36 into eq. 5.37 and changing the variable
of integration from v to Au, we have

” ”(1:)HWWLJ]:
2
= 3. (5.3a)
met:

The line profile it”. defined by alJ = orb”. is therefore

v = ————-.
V/(41r2) 5.39
(D (AV)2 + (11/471)2 ( )
In the classical model. the spring has only one natural frequency, whereas elec-
trons in an atom can be in an infinite number of electronic states and can undergo
different transitions at different frequencies 1:0. This effect is approximated by a sys-
tem of many springs. each having a fractional contribution to the total transition:

2
a”: (m )fav. (5.40)
nice

The fraction f is known as the oscillator strength and has a different value of each
transition. Comparing eq. 5.40 with 5.10 and making use of eq. 5.14. we can separate
the oscillator strength into two components. an absorption oscillator strength defined
by
m c hv
.61 = ”:2 GB}: (5-41)

and an emission oscillator strength defined by

mec hv
--_ —-——B . 5.42
f” we2 4:: U ( )

Since 3} 31-,- = g,- Bil (eq. 5.8). we have

0‘
ij1t = ‘3tft‘j- (5-43)
132 Line Radiation from Atoms and Jon:

For the H atom. which has one electron, the sum of the fit and fij values over all
transitions should be equal to unity. Substituting eq. 5.41 into eq. 5.9. we have

A-- =
Ej _
Haze-2t:2
fji- (5.44)
U 3i 711,63

A strong line (large f value) therefore also has a corresponding large A Value. The
absorption coefficient (eq. 5.16) can be expressed in terms of the oscillator strength
by
"t. 2
av = ( — 51—) nifji¢w (5.45)
Sin}

By writing the absorption coefficient in this form. the equations will have the sang
form as in the classical model. and all the quantum mechanics is hidden in the
evaluation of the values of the oscillator strengths.
In the semiclassical quantum mechanical scheme. the transition probabilities of
atomic transitions of simple atoms (e.g.. H) can be calculated by the time-dependent
perturbation theory. in the dipole approximation, the oscillator strength is given by

8:! 2m, u“- 2

fjt = vl l¢r Ifl'ltfijll . (5.46)

where er is the electric-dipole operator and c). and d5..- are the wavefunctions of the
initial and final states, respectively. Equation 5.46 can be rewritten as

4 Tflwulttfirlrltfijlnz
f}: — 3 hp”- ! {5-47)

where mu- = 2:71;”. Therefore. the oscillator strength can be considered as the ratio
of the kinetic energy of the electron to the energy of the radiated photon. For allowed
electric-dipole transitions. the oscillator strengths have values of the order of unity.
Experimentally. the oscillator strengths can be determined from the measured
emission intensities of the transitions. However. such measurements are dependent
on the temperature and density of the source. The theoretical f values of many light
elements have been calculated under the Opacity Project (Section 5.”). Theoretical
values of transitions in heavier elements are less reliable because of the need for
relativistic corrections and deviations from the H coupling. Once the oscillator
strengths are known. the absorption coefficient can be obtained from eq. 5.45.

5.7 Scattering Cross Sections

The same classical oscillator model can also be used to describe the behavior of
light scattered by a medium when the light frequency is different from the resonance
frequency. Making use of eq. 5.25 and eq. 5.34. we have
 5.7 Scattering Cms: Sections 133

__ (41112) (3.9sz) m2
u - nice 3 m,c3 (at: — (92)2 + yz’tt)2
fine“ to“
=
stage (mg - (02): + yzwz ( 5.48 )
For (at — coo) >> y.

Bne‘ l
a = 5.49
” M364 (to: _ I)2 ( )

At low frequencies where to << can,

81m“ ) a)“
av = — (5.50)
(3"!36‘ «)3
«1'5 (ssh
This process is ltnown as Rayleigh scattering. Its strong wavelength dependence
means that blue light is scattered much more than red light. and Rayleigh scattering
of sunlight by molecules in the atmosphere is the reason why the sky is blue.
At high frequencies where tr) >> coo, eq. 5.49 becomes

a— 8ne4
”'h?
2 1
=E(‘). mm
3 um:2

This is known as the Thomson cross section and has a numerical value of 6.67 x 10‘”
cm]. Unlike Rayleigh scattering, Thomson scattering is independent of frequency.
The expression inside the bracket ezlmgz is known as the classical electron radius
because it is the radius of a charged particle for which the electric self-energy :2] r
is equal to the rest energy m,c1. In this approximation. light is primarily scattered by
the electron. so eq. 5.52 is also referred to as the electron scattering cross section.
When an incident photon encounters an atom with internal energy states. the
scattering cross sections are enhanced at the resonance wavelengths. If there is an
exact coincidence of the frequencies between the incoming photons and the energy
separation ofthe internal states, fluorescence will result (Section 5.13). Ifthe energy of
the internal state (E0) is less than that of the incoming photon (I: no). then a scattered
photon of energy hvo — E0 can be produced. This is known as Raman scattering.
We should note that while Rayleigh scattering leaves the frequency of the incoming
photons unchanged, Raman scattering causes a shift in frequency in the scattered
photons. The magnitude of this shift is called the Roman shift.
134 Line Radialionfi'om Alarm and Ions

3P

0 v! 11032

0 VI 21038

IS

Figure 5.16
A schematic diagram illustrating the Raman scattering of 0 v1 photons by neutral H (3113de
from Schmid. HM. 1989.144“. 211.1.31).

An example of Raman scattering observed in the ISM is the scattering of the 0 v1

doublet 11033 (In;2 Jsm) and A 1032 (213;;2 Jsm) by neutral hydrogen. Since
this doublet is close in wavelength to the Lyfl line, the Raman scattering cross section
is enhanced. From the conservation of energy. the Raman-scattered photons will have
energies of IN — lav.” (Fig. 5.16). Using vacuum wavelengths of the 0 v1 lines
from Table 5.2 and the index of refraction in eq. 5.53, we find that the corresponding
wavelengths in air of the visible lines are 6825.00 A and 7031.95 A for the 1032 and
1038 lines. resPectively. These wavelengths compare well with the rest wavelengths
of the broad emission features seen at 116825.44. 7082.40 A. respectively. After the
Raman scattering. the H atom will be left in the 25 state and eventually decay by
collisional processes. or by the two-photon continuum emission (Section 6.2).
p.-
57 [a
3
II

2.400990 1-: 10-2 + 1.7455? x 104

=1+B.06051x10'5+
132.274 — (104 51/1,“)! 39.32951 — (10‘ An”)!
(5.53)
 5. 7 Scattering Cross Sections 135

105-12
21111111 §| 2111111 3[
60542 L [\ 1111131611995 M1. Hopkins 113111995. '*
' Miriam-13
305—12

- 1 mm 1 , 1, 2.05.13
035.00 V1016 Cyg V1016 Cng - 3-05-13
1111731711995 Mt. Hopkins 31411995

F111: (ergs cm”! s“ A ')

1-T‘ 1013—12 '
1a 1 i 405—13
4' K.. . 9_JL_~ 1/1
E 0.0% 1 ._ . 1 . . _1_ 11 . . 0.0m
. AG Dre 1113 Dre
3 11111311611995 M1. Hopkins 31411995

5
I: ”5-”
- \K /\W LN 905—13

0.019100 “t + ' ' 7‘" 505—13

RRTeI WRETeI
605—11 —\HUT311211995 1111f. 8116111111 5111111995 — 6.0E—l3

105—11 — J‘sA“ f") 105—13

\. 1‘1‘ . . I Jer—j ‘ |
0.05410 J-i‘ ”A 00111-00
1020 1040 61100 6900 1000 7100
Wavelength [A] Wavelength [A1
11191125.”
Simultaneous spectra of the 0 v1 (left panel) and Roman lines (marked by vertical bars in the right
panel} obtained from the HUT and ground-based telescopes (adapted from Birriel et al. 2000.11.91.
M5. 1020).

Assuming that the original line width of the 0 v1 lines is preserved. the lines will
be broadened by the ratios of their UV and visible wavelengths. or about a factor of
6.7.
The eficiency of this process can be determined by simultaneous observations
ofthe UV and optical lines. Figure 5.1? shows the span of the 0 v1 and Raman
scattered lines from the Hopkins Ultraviolet Telescope (HUT) and ground-based op-
tical telescopes. respectively. From the measured line fluxes, the observed efficiencies
range fiom 610 15% for 111032 —+ 6825 and 2 to 13% 1611110311 —> 7082. The higher
efficiency of the former can be understood as the result of a higher scattering cross
section for being closer in wavelength to the Lyfl line.
136 Line Radialionfiom Atom and Ian:

5.3 Line Broadening

All atomic and molecular lines resulting from b—b transitions are not infiniter Sharp
and have finite widths as a result of various broadening mechanisms. These includr;
radiative broadening due to the finite lifetime of energy levels. collisional Widening
as a result of shifts in emission frequency due to collisions with other particles during
the emission process. and. most significantly. frequency shifts due to the motions of
the emitting atoms through the Doppler effect.

5.8.1 Natural Broadening

For an optically thin absorption line in a stellar atmosphere or an interstellar cloud,
the change in intensity All. of the line is proportional to its optical depth 1'... which in
turn is proportional to the absorption coefficient x... If the line profile is given by the
Lorentz profile. the frequency at which the intensity is half of the maximum occurs
when the two terms in the denominator of eq. 5.36 are equal:

y
A v _ __
4" (5.54)

This is referred to as the half width (Avi) of the absorption line. Substituting eq. 5.25
into eq. 5.54. we have

I 2 £20.13
15”; — (a) (am—c3) (5.55)

= 2 x 10-23 sec v3. (556)

Expressing the half width in Wavelength units.

C
A1; = EAL}

2
= 3—.“ (5.51)
3 mcc2
= 5.9 x 10 5A. (5.53)
This value, called the natural width. is intrinsic to the transition and represents
the minimum width of any spectral line. The full-width-half—maximum (FWl-IM) i5
2Mi = 0000113 A.
In quantum mechanical terms. the Lorentz profile and the natural width can be
understood from the point of View that the energies of both the upper and lower states
have uncertainties as a result of Heisenberg's uncertainty principle AE At ~ h. Since
the lifetime of a state (At) is finite, AE qé 0 and the transition frequency does not
have a single value but has a finite spread. The quantum mechanical analog Of the
 5.8 Line Broadening IJ‘I

Lorentz profile is the same as eq. 5.36 except that y is replaced by l‘. where

n} = Z is},: + Z A”. (5.59)

lr<j Luci

5.8.2 Doppler Broadening

1he width of any actual absorption line can be bnoadened further by a variety of
proceSses. such as turbulence and pressure. In interstellar clouds. the broadening
of spectral lines is dominated by random motions of the atoms or molecules. Such
motions along the line of sight will introduce Dappler shifts. resulting in the creation
of line wings on both sides of on.
An atom with a line-of—sight velocity component of tiz will cause a frequency
shift given by the Doppler formula:

—=— = —. (5.60)

In an ensemble of atoms at kinetic temperature T. the distribution in u, is given by

the Muweliian distribution:

N (Ur) dug I U: do,

--—- _— —-—- exp —— —, 5_61
N {fr ( a2) a ( )

where N is the total number population. at is the mass of each atom, and cr is defined
by

.2523m
(5.62)

As light of intensity It passes through a layer of atoms at temperature T. the

velocity distribution of the atoms will cause line absorptions at the line center v0 as
well as in neighboring frequencies. Under optically thin conditions. the amount of
absorption at frequency v is proportional to the number of atoms at a specific velocity
at. Hence. the intensity absorbed over a narrow strip of frequency dv expressed as a
fraction of the intensity absorbed over the entire line is

ac — lu)dv _ N(v,) do:

[mac — may ' N
= éei‘fihz’d—a’fi. (5.63)

Defining the Doppler width AvD (and the corresponding AM, in wavelength
units) as
an:

AUD __ Alp
= , (5.54)
1-’o 10
138 Line Radiation from Atoms and Ian:

we can show that

v, _ Au
3 - AUD . (565)

Substituting eq. 5.65 into eq. 5.63. we have

(16—. Iv)d|r' l —(AUIAIJD)2 d”

—— = —e —.

fac — ndv J? Aug (5'56)

The nonmlized line profile is, therefore. given by

¢ = (I: -' In)

" for. - I)du
l _ 2 l
= 7?: (AV/AU”) A—UD. (5.67)

We can see that fovdv = I when integrated over the line from Au = —eo to m. =
+oc. At the line center Av = 0. so

¢ —_1..._l_. 56
”—fiAVD. ('3)

The frequency at which the line intensity is half of maximum (defined as Avm)
can he found by setting 19., to half of its maximum value:

5 = (mm/MD)? (5.69)
Hence. the full-width-half—maximum (FWI-EM) of the line is

2mm = 2./ Av}, 111(2)

= 2/731 mm»...
C m
(5.70)
For the J = l -+ 0 line of C0 (v0 = 115 GHz) in a molecular cloud of kinetic
temperature 50 K. the FWHM of the line due to the Doppler effect is IDO kHz.
Although the broadening is relatively small. it is still much larger than the natural
line width. which from eq. 5.56 is 0.5 Hz.
Expmsing the half width in wavelength units. we see that
L'
Ali =—
”2“”? . 1
(57)

For Hfi line (A0 = 4860 A) in a gas cloud of 10,000 K. the FWHM is 0.35 A. or 3003
times the natural width.
 5.9 17:: Wig-t Profile 139

5.9 The VOiB‘ mm”

In order to calculate the profile produced by Deppler broadening. we begin with the
Lorentz profile (eq. 5.36):

in:1 I" 1
av: (5.72)
nice 4n2 (v0 + Eva — u)2 + (32):.

where the damping constant 1" includes contributions from radiative. collisional. and
pressure broadening efl'ects. Assuming that the velocities of the atoms or molecules
are distributed according to the Maxwellian distribution (eq. 5.61). the absorption
cofiicient is therefore given by the sum of all the contributions from the Lorentz
profiles of each of the moving atoms:

x” =f a,N(u,) d0,
a:

1,2
_::e2N r °° 1 up(-;:) d 573
-— f—z u 2 I‘ z u. (' )
nu: 4» —mfia(vo+;uo—u) HE)

Making use of the Doppler widths as defined in eq. 5.64 and the relation eq. 5.65.
we have

:33”
_
I" 1 f“
—.
°"P('(§‘o)z) edit:
. 5.74
K” mac 4n2fia 2 )( )
— u— A (T4103 2 ( Do
an [(3% _ ATE) + AVD ]AUD

By defining the following dimensionless variables.

Au
3' 5 -—
AUD (5.75 )

U — 1’0
= 5.76
u Av” ( )

a a W4", (5.77)
ADD

we can write the absorption profile per atom (av = rv/N ) as

_ uez f ( a )j’” exp(-y2)

a”_(m¢6) (Me) It“ -mtu—y)1+a2dy
=alH(a. u). (5.78)
140 Line Radiation from Alarm and Ion:

where

a = met:
E ;;-AvD J1? (5.79)

and
an 2

”(E u). a convolution of the Lorentz and Doppler profiles, is known as the “”8!
pm e.
Near the line center (v = no and u —> O), the contribution to the inlcgral in «1.5.80
is dominated by y 2: :4. Therefore,

a -2 °° dy
H . 2 — " —
(a U) (3): [no 324-02
—|r2
=e - (5.81)
The line profile near the center therefore has a Gaussian shape.
2

av =ale_(fig) . (5.32)
and is known as the Doppler care. In the line wings away from the core (it >> 1). the
integral in eq. 5.80 is dominated by y ~O because the rapidly decreasing function
a": is the numerator. Assuming 0 << I.

(5.33)

= — ——. 5-34
mec 41r2(v — no)2 ( )
We can see that eq. 5.84 is a limiting case of the Lorentz profile (eq. 5.36) and that the
line wings of the Voigt profile are dominated by radiative (and collisional) damping-
 5J0 Equivalent Will and the Curve of Growth 141

As an example. we consider the calcium K line (1.0 = 3933 A) in the solar

mospherc (r = 5700 K). Since me. = 40m". 11 = 1.5 km s-1 and mo has a value
of 3.9 x 109 Hz. The value of 1‘ due to the sum of all spontaneous radiative u'ansitions
is 1.72 x 103 s“. If a stellar atmosphere. collisional broadening due to gas pressure
dominates over radiative broadening. If we assume a total value for l" of 1.6 x 109 s".
a = F/47rAvD has a value of 0.033. The u-ansition from the Doppler core to the
Lorentz wing occurs at ("I ~ A . or u = 2.4. At this point (v — yo = 2.413%).
the depth of the profile at this potnl relative to the line center is e441, or 3 x 10—3.

5.10 Equivalent Width and the Curve of Growth

The concept of equivalent width is a measure of the total strength of an absorption
line and is defined as

_ fline(Ff-' " F9) d”

_ —————Fc
Wt

F
= l——|I d. 5.85
[line( F) v t )
where F, is the flux of the line at wavelength v and F, is the flux of the continuum.
Over the small range of wavelength covered by the line. i‘i‘c can be considered as
a constant. Therefore, W” is the width of the absorption line if the line profile is a
rectangle. For an optically thin line.

1» = new
~ [C(l - z”). (5.86)
where 1-,, = f hands. Therefore,

WU ~ N j avdu

2
= (1” ) fN. (5.37)
mac

where N = f nds is the column density. The equivalent width in wavelength units
(W1) is related to W, by

2
= ( “e ) 12fN. (5.83)
"I
142 Line Radiation firm Atom: and Ions

For a strong line where all the continuum photons are totally absorbed in the line
center. further absorption can occur only in the line wings. From eq. 5.84, We have

1n:2 T‘lttrr2
flu (in—,6) f A122 - (5.89)

From eq. 5.86.

11:2 l" l
“Iv—f [1 —exp [(-m—OE) Nf (411-7355)]ld9

= (M) f (w) p . t .
ne2
-—— N
1‘
—-— l —
_1/ z
“ d . (5.90,
where u = J :45 fi. Since the integral in eq. 5.90 is just a number, the equivatem
width is given by

W, 0: Nfl" (5.91)

and

wJL a: tR/Nfr (5.92)

in the saturated line limit. This change of behavior from linear to square-root depen-
dence on column density is called the curve ofgmwth.

5.11 Recombination Lines

Since the H atom cannot be excited by collisional means under interstellar conditions.
and there is also very little background interstellar radiation in the visible region avail-
able for excitation by absorption. the only way that an H atom can be found in an
excited state is by recombination. After each recombination. the atom will cascade to
lower states by a series of spontaneous emissions. These lines are called recombin-
tion lines. Several examples of H recombination lines are shown in Figure 4.1.
The spontaneous transition probability Anmrg for electric-dipole transition in
hydrogenic ions is given by

64Jrr“v3 man“. 8’) 2 2 °'° r 2

W = Erin—+1 “0 [/0 R“ (:0) ”fl‘” ' “'9”
where

v = R122 (l2 — Ric) (5-94)

:1
 5. U Recombination Lines 143

and R“ and R”: are the normalized radial wavefuncu'ons of the initial (i) and final
(j) states. respectively. 2 is the nuclear charge. R2 is the Rydberg constant. and a0 is
the Bohr radius. For electric-dipole transitions. the selection rule is 8 = I." :t I.
For the H atom. the integral in eq. 5.93 can be evaluated analytically. For example,
the radial wavefunctions for the Is and 2p states are

Rm =7ao_3flre""°° (5.95)

and
a—S/Z
Ru = — 3/27 :2 e-WO. (5.96)

respectively.
The integral inside square brackets in eq. 5.93 is therefore given by

c” r 1 °° r 4 _3,. r
n — R d =-— _ med (-—). 5.97)
jti l"(30) 2" r J3 o (do) 8 do (

Since f0" 1"2‘" (1;: = l"(n + Did“. the integral above has a value of —§.(§)5.
Substituting this result into eq. 5.93, we have the spontaneous emission coe cient
for the Lya (2p -- ls) transition:

26n4v3 1 22(2”)
A =— - a —
2"“ 223th (3)8 ° 39
22lfl4v3 2 2

allhclm°
= 6.263 x 10' s-'. (5.93)

Making use of the relationship between Aij and fj,- (eq. 5.44) and the expression
of the Bohr radius (eq. 4.l6). we can obtain the oscillator su-ength of the Lyman a
line from eq. 5.98:

213
ft: =:—: (m) - (5.99)

Since 3: = 2(28 + l) = 6 for the 2p state.

6 213
f12=§ (fl)

= 0.4l62. (5.100)
144 Line Radiation from Alarm- and Jon:

Table 5.3
Oscillator strengths for some of the lower transitions of H

"I- 6I "2- 52 f "1‘ 51 "2- ‘2 1'

LO 2.] (Lyn) 0.4162 2.1 3.0 (Ha) 0.01359

3.! (LYfl) 0.079l0 3.2 (H11) 0.6955
4.1 (Lvy) 0.02899 4.0 t'Hfl) 0.003045
5.1 (Lys) o.0|394 4.2 (H19) 0. ms
2.0 3.] (Ha) 0.4349 5.0(Hy) 0.W1213
4.] (HH) 0.1023 5.2 (Hy) 0.04437

The A coefficients of the other members of the Lyman series can be similarly calcu-
lated using the H atom wavefunctions. and the rest of the oscillator strengths can be
summarized by the following expression:
)2i—4
--r...

rec—“V" (5.101)

The values of the spontaneous decay rates (expressed as oscillator strengths) for
several lower transitions of H are given in Table 5.8.
The total transition rate (AM) can be obtained by summing over the orbital
angular momentum states:

I
A“. = :5 Em + ”Addy... (5.102)
(1‘

Similarly. the total oscillator strength (1;...) is given by

ffl'fl = fi 2(2‘8 + Dfn't—bn!" (5-103)

1.6
Since three separate transitions contribute to the Ho line (see Fig. 4.1).

1
f3 ‘1 Eunflr—bSp + (3)].2p—b3: + (3)f2p—b3n']

= fi[(1)(o.4349)+ (3)(o.01359) + (3)(0.6958)]

= 0.6407. (5.104)

Similarly. f", has a value of 0. l 193 and ny has a value of 0.04467.

 5.1] Recombination Lines 145

Although the f values of the other transitions of the H atom cannot be written
in a simple closed form. the following expression was derived by Kramers using old
quantum theory:

64 l I
'i='——“'—'— ll
___. _ 1105
’3 afin2j2[1_r]2(r313)3“’ ( )
F7 :1
The Gaunt factor for b—b uansition g“, was added to the Kramers formula to include
quantum mechanical effects.
Whenwesumoverthe oscillatorstrengthstincludingemissionoscillatorstrengths)
over all transitions. we obtain the total number ofelectrons in the atom. This is known
as the Thomas—Kuhn sum rule. Specifically,

3; °°
Zfrm+2ffjr+ o frtdk=n. (5-106)
nth-i i>j 3'

where n is the total number of electrons in the atom and the third term in eq. 5.106
represents b—f absorption resulting in a loss of an electron. In the case of H. the sum
over all f values for each of the series (Lyman. Balmcr, etc.) should result in a total
of l as the H atom has only one electron.

5.11.1 Optical Depth of Lyman a

Since the Lyman transition decay rates are much higher than the recombination rates.
any recombination will quickly decay to the ground state. For practical purposes. all H
atoms in the ISM can be assumed to be in the ground state. and the second term in the
absorption coefiicient in eq. 5.15 can be ignored. Assuming then-rial broadening at a
temperature of ~ [0“ K. the absorption coefficient a” for the Lyar line is ~ 10-13 cm2.
The mean free path for a Lyar photon. given by l/nHau. is extremely short compared
to typical sizes of interstellar clouds. and a Lya photon can expect to travel only
a small fraction of the nebular size before being absorbed by another H atom. The
corresponding optical depth in the line is
L
r=f nlaudr (5.10?)
o

.t 3 x 105( "H 3) (L/pc). (5.103)

cm

Comparison with eq. 4.24 shows that the Lyor line optical depth is 10‘1 times the
optical depth at the Lyman limit for continuum photons. In other words, if the nebula
is ionization bounded (Section 4.6), the optical depth of Lyor is > 10‘.
The high optical depth of the Lya line implies that the Lyot photon will be
absorbed and reemitted (i.e.. scattered) many times. Since the H atoms have a spread
in velocities. some of the Lyon photons will be scattered into the line wings due the
Doppler effect. As the optical depths in the line wings are much smaller than in the
146 Line Radiation from Atoms and lens

line center. these Lyn photons can escape from the surface of the nebula after many
fewer instances of scattering than those in the line center. If dust is present in the
nebula. some Lyn photons will be absorbed by the dust before escaping and will play
a role in the heating of the dust component (see Section 10.4).

5.11.2 Population Distribution of the H Atom

Since an ionized nebula is often optically thick to the Lyman series photons. the level
population of the H atoms is affected by self-absorption. and a full radiative transfer
calculation is needed to determine the population distribution. However. if we take the
extreme case that the entire Lyman series is optically thick. then the net effect is that
every Lyman series photon is eventually converted to photons of lower H series (¢.g__
Balmer. Paschen) plus a Lyn photon. Take the example of Lyfi. After it is emitted,
it will be reabsorbed by another H atom until the atom takes the route of cascading
to the n = 2 state (by emitting an l-la photon) and then to n = I by emitting a Lyn
photon. Similarly. a Lyy photon will be converted to Pau+Ha+Lyn or Hfl+Lya after
several scatterings. The net effect is equivalent to the total absence of the n = 1 state.
The Lyn photon will be scattered from atom to atom until it escapes from the nebula
or is absorbed by dust. but it will have no efl'ect on the population distribution of the
remaining states. This approximation (called Case B) allows for the solution to the
population distribution by including only spontaneous emission and recombination in
the statistical equilibrium equation (collisions are not important as we noted before).
The other approximation (called Case A) corresponds to the case where all the H
transitions (including the Lyman series) are optically thin.
Under Case A orCase B, the absorption/stimulated emission terms can be omitted
and the statistical equilibrium equation for each level n has only three terms:

on n-l
Z Z "it'Ar'E’th + "pneanf(Te) = "a: Z Z AntJt'Vv (5.109)
l=n+l r! j-lorI r"

where the first term on the left represents cascade from levels above, the second
term on the left represents direct capture of a free electron. and the term on the
right represents cascade to levels below. The sum on the right-hand side begins with
j = l for Case A and j = 2 for Case B. If the population distribution is in LTE, the
population in each excited state at will be given by eq. 4.34. In general. the actual
population can be written as

h: m e h ”"1 H'. (5-110)

"n: = bntnpneae + l) (m)
f

where the dimensionless coefficients b", represent the degree of departure from the
thermodynamic equilibrium distribution.
 5.“ Recombination Lines 14"

Substituting eq. 5.] 10 into eq. 5.109. we have

3 2
an! (Zill'lw'ek're)ll e-hvnffl',+
2C +1 I!2

°° 25‘ + 1 ""
Z Z: blC’Ar't'mt (26 + 1) €“'"'”"”"‘ = but 2 2 Annie"-
r=n+i t' j-lar2 I"

(5.111)

which can be solved iteratively to obtain but for each level.

5.11.3 Recombination Spectrum of H

In the approximation that the population distribution is mostly determined by recom-
bination. the resultant spectrum is called the recombination line spectrum. Once the
population distribution of the H atom has been detcnnined. the emission spectrum
can be calculated. Specifically. the emission coefficient of each of the emission lines
of H can be obtained by substituting the solutions of "nt from eqs. 5.111 and 5.110
into eq. 5.11. The emission coefficients of the recombination lines are often expressed
in the form of efi'ecrive recombination coefiicr'enrs. which are defined as

’1 If)“. r 1
mg”; m (5.”2)
npnE

for the recombination lines n! —> n’t’. Note that n", is a function of a and A and is a
function of T,. The name “effective recombination coefficient" is unfortunate because
it often gets confused with Ihe recombination coefficient on, (eq. 4.41).
Although collisions are not important in the excitation of H. they are important in
shifting betteeen different angular momentum states of the same principal quantum
number n. Such transitions will involve no energy change. and can involve collisions
with both protons and electrons. Forcxantple. at [0" K. the p—H collision cross section
for 23 to 2P is ~ 3 x 10—"J cmz. The addition oftlte collisional terms to eq. 5.109 will
provide a more accurate solution. Examples of effective recombination coefficients.
calculated taking into account collisions between different it (in particular An i l)
and L states. are shown in Table 5.9.
For T, = [0‘ K. of}; has values of 2.04 x 10"" and 3.034 x 10"4 cm3 sec—1.
respectively. for Case A and Case B. The value is higher for Case B because the higher
Lyman lines are recycled to Balrner photons. The efiecuve recombination coefficients
decrease with increasing temperature because more energetic electrons are leg likely
to be captured by the proton (eq. 4.39).
The strengths of Balmer lines can deviate from the Case E values if collisional
excitation is significant. Since Lyn: is optically thick. the first efl'ect of electron
140 Line Radiation from Atoms and (arts

Table 5.9
Emission ooeflicients (relative to jag) for some of the lower transitions of H under Case B for
r, =10“ K. n, = 10‘ cm-3
t' jj 2 3 4 5 6 7 3
3 2.85
4 LCD 0.332
5 0.469 0.162 0.0773
6 0.260 0.0901 0.0447 0.0245
7 0.159 0.0554 0.0275 0.0158 0.00929
8 0.105 0.0365 0.0 l 81 0.0105 0.00650 0.113402
9 (1073.1 0.0254 0.0126 0.00726 0.117456 0.00299 0.00192

Source: Storey and Hummer. 1995. MNRAS. 271 41.

collisions is an increase of the level population of n = 3 due to collisional excitation

from n = 2. This results in a larger Ha to H5 ratio titan the Case B value of 2.83.
In terms of the effective recombination coefficient. the integrated emission coef-
ficient (j) is

j =fjvd”

nenpamhv
4” (5.113)

For the H5 line in Case B. 411'} is 1.24 x loffinenp erg cm 3 s". From Table
5.9. the corresponding value for Bracken y (n = 7 -— 4) is 3.41 x 10‘27ntnp erg cm"3
3". Sometimes it is preferable to observe Br 1/ instead of HB because there is
less extinction in the near-infrared pan of the spectrum (Chapter 10). Examples of
the H recombination lines in the infrared are shown in Figure 5.18. Higher-order
recombination lines of H can be detected in the mm or radio pans of the spectrum.
Some examples of the frequencies of some H and He recombination lines in the radio
region are listed in Table 5.10. While the radio recombination lines are easily detected.
mmlsubrnm recombination lines in 1-1 11 regions such as the Orion nebula are often
crowded out by the stronger molecular rotational lines (Section 7.4).
The H recombination line model can be checked by observing a wide range of
recombination lines. For example. in MWC 349. the H no: lines can be observed from
radio to infrared to Optical. covering values of n up to 100 (Fig. 5. 19). The hump above
the theoretical line (from aboutn = 7 to 36) is believed to be the result of maser action-
 5.“ Recombination Line: [49

E 'é s E E
7_l"—T—' T—‘
l 54
"3-5 '
9-5
M

12-5 i
500”” erg, 1-:111'1 s‘I pm")

13-5 3-5

14-5 '
l——u-
O
N
.—
§

l9-6 .
_l—'—'|_'

a..16—615_6

130 ' l3-6

170 MWC 349

150 L._ .1.__l_1_J__.-__ L4._.1 _1__E___1_,L___L _J__1_f1_;___

2.3 2.5 2.7 2.9 3.1 3.3 3.5 3.7 3.9 4.1 4.3
Wavelength (,um)

Figure 5.18
[SOSWSOI spectrum of the emission—line star MWC 349 showing three separate series (labelled 1' — u.
when: n = 4 is the Bracken series; n = 5. Pfund: and n = 6. Humphreys) of the H recombination
lines.

For a constant temperature. constant density. optically thin nebula of radius R at

distance D. the total observed Hfl flu: is given by eq. 2.85:

4n} 4IrR36
Fna= 411132 ( 3 ) (5.114)
R3€ “-
= (332-) hvflflnenpafim. (5.115)

where thefillingfactor. 6. is introduced to take into account the fact that the electron
density may not be distributed uniformly over a sphere. For example. a shell of
thickness AR = 0.2}? can be approximated by setting

_ 411' R215. R
g1? R3
= 0.6. (5.116)
Thble 5.10
1-1 and He mombinnfion line frequemies (in MHz)
———.__

n H rm H 11.6 1-! :17 He M He ufi

40 99,022.96 191.0514 276.7453 99.15332 19l_|35_3

50 51,071.62 99.2252 144.6783 51.092.43 99265.66

60 29.70037 57.975.24 84.914.41 29.7[147 57.99336

70 [8.769.16 36,761.72 54,019.94 [8.77631 36,776.10

80 12,607.08 24.755.74 36.46735 12,612.22 24.7618]

90 8.872.569 17.457.39 255166.77 8.876.184 17.46450
10) 6,478,760 12.767.90 18,874.76 6.48141“) 12.773.“
[50 1.929.162 3.820.374 5.674.624 1.929.948 3.821.931
200 815.8886 1.619.690 2.411.642 816.2211 1.620350

300 242.3470 482.2905 70.8623 242.4457 482.4870

Wed from Lilley and Palmer [968.441.15. us. 143.

1 pm 10m: 100 ,um I nun 1 cm

I I I I
m.
. \ MWC 349
‘tn H na transitions
16” 1- \E -
. \\

". u

.. 10-" 1— "
\ II
1'" _
E L D .
3_ L \ m
1-1."I ' m
10‘" - '\ g] -
‘92
10-21 _
KBR fl
E.\
D. ‘l
. 1 4. . n 1 ._l 1 . L 1

3 10 30 100
Quantum number I:

Figure 5.19
Theflun oanaIlinesfromtheinfraredtothermfioiuMWCM9asumncflmof
quantum number n. The ISO and mum-based measurements are shown in solid and open
symbols. respectively. The doued line is a Case B recombination model for 7'£ = 1500 K and
n, = 10' cm" (fmm “mums et a1. 1998. AM. 333. L63}.
 5.12 Collisionally Excited lines 151

For R =O.l pc. D= 1 kpc. e =o.s. up =103cm-3.n. = imp. r, = [0‘ K. the

total H3 flux under Case B is 9 x ID‘H erg cm‘2 s".
Ionized helium (He+) has a similar electronic structure as H and its recombination
lines can be calculated in the same way as H. For neutral He. separate calculations
have to be done for the singlet and triplet states as transitions cannot cross between the
two. For the singlet state. the effective recombination coefficients can be calculated
under both Case A and Case B as was done for H. For the triplet state. since there is
no transition to the groand state. Only Case B applies.
Many of the recombination lines of heavy elements occur in the ultraviolet and
are observed by the IUE and FUSE missions (see Table 5.1). Because of the low
abundance of heavy elements. these recombination lines do not suffer from optical
depth effects as in the case of H and He recombination lines. and can be used as
a diagnostic of the density and temperature of the emission region. Therefore. the
recombination lines and collisionally excited lines of metals provide complementary
methods for the derivation of elemental abundances in nebulae (Section 5.19). With
the increasing number of recombination lines in the UV and collisionally excited
lines in the infrared available for observations. the accuracy of elemental abundance
determinations is much improved from those obtained with optical spectroscopy
alone.

5.12 Collisionally Excited Lines

Although the abundances of metals are much lower than that of hydrogen. collision-
ally excited atomic lines in galactic nebulae. in particular planetary nebulae, are as
strong as the H recombination lines. This is because collisional processes are sev-
eral orders of magnitude faster than the recombination process. Collisional excitation
to low-lying metastable states and their subsequent decay via magnetic-dipole ot’
electric-quadrupole transitions lead to emission lines that are commonly referred to
as forbidden lines. Since the identification of the forbidden lines of 0 by l. S. Bowen
in 1928. forbidden lines from ions of common elements ranging from N to Fe have
been detected. Recent sensitivity improvemean as a result of the use of CCD detec-
tors have led to the discovery of emission lines of krypton (Kr. Z = 36). xenon (Xe.
Z = 54). and other less abundant elements in the 4th. 5th. and 6th rows of the periodic
table. Probable identifications include selenium (Se. 2 = 34). bromine (Br. Z = 35).
rubidium (Rh, 2 = 37). and barium (Ba, 2 = 56).
While strong forbidden lines from ions such as 14"". 0+. 0“. Ne“. Ne”, Al2+.
. An”. and Mg4+ are widely observed in galactic nebulae as well as active
galactic nuclei. forbidden lines are not the only collisionally excited lines in the
nebular spectrum. A number of near-UV permitted lines of metal (e.g.. C II. C IV,
N v. Mg I. and Mg 1:) are also collisionally excited and are very prominent in nebular
Spectra observed by the IUE (Table 5.1). Some of these lines can be seen in the tU'E
spectrum of Hu [-2 shown in Figure 5.20.
The collisional cross section for transition from level j to level i is inversely
proportional to it2 above the energy threshold EU and is zero below. The collisional
152 Line Radiation from Atoms and Ian:

SWP13945 Hu 1-2
'— —l— I I w— r
6.0- "3'” I He it
C “,1 M640

11548.”)50
5.0- 10'”

C 111]
- 10'”
P
o

Ll907.l9t19
Calibrated flux

1/ La Geomtona

- IO'”
LII
o

N W]
114334431
- 10-”
r4
o

Nv 1|”;le
112311242
,-
5' W
+ Q or
1.0- 10-”

[400
1.1. l

[500
Wavelength (A)

Figure 5.20
IUE Short Wavelength Prime (SH/P) spectrum of Hui-2 showing several collisionally excited lines
in the UV (C IV. N v). The vertical scale is in units of erg crn‘2 s‘l A". (Figure courtesy of W.
Feibelrnan.)

cross section can be expressed in the following form using a dimensionless quantity
called the collision strength. 91,-:

hit 91
aj;(v)=(nag) T—Ez —’ (5.117)
Ime" 3}
2 .
__. _"___" 9.11. (5.118)
4321113111 3}

Where a0 = h2/4n2m,e2 is the Bohr radius (eq. 4.16) and 1116.; = 2n2e‘m,/h3 is the
Rydberg constant (eq. 4.4). The collision strength 91'1' for a transition by electron
impact excitation can be calculated theoretically from scattering theory.
For levels within the same multiplet. the collision strength of each fine-structu'e
level I is related to the total collision strength of the multiplet by

(21,- + 1) (5.119)
Q-- S-L-J-.S-L J,- =————————- R):(5)L).S,-L,-),
"( J J 4' ' ‘ ) (2L,+1)(2s.-+1)
 5.12 Collisionally Excited Lines 153

3P3 Isa _ 3P3 2P

Collision mph

0 ...|4._.-|4Liulgrl4_l.
0 0.2 0.4 0.6 0.8
Final electron energy (Rydberg)

Figure 5.11
Collisional strength for the 3:23p‘ ‘5’ - 3.523;)3 2P" transition of S u. The solid line is the calculation
of Ramsbottorn er al. (I996, Ar. Dara Nucl. Data Tables. 63, 51) and the dashed line is by Cai and
Ptadhan (1993. ApJS. 83. 329].

provided one of the states (i or j) is a singlet (S = 0 or L = 0).

The collisional strengths consist of resonances that vary rapidly with energy
(see Figs. 5.21 and 5.22). However. in astrophysical situations where the colliding
electrons have a range of energies. the effects of the resonances are averaged out.
The collisional excitation rate for an ensemble of electrons at temperature T, can be
obtained by averaging over the Maxwellian distribution:

gm) = f Ina-sumo do. (5.120)

where um = (25,-,/m,)W. Substituting eq. 5.118 into eq. 5.120, we have

3.629 X 10-6 &e_EU/&Tf

Cjt' = _
Telfl g;
cm 3 s -l . (5.121)
154 Line Radiation from Atoms and Ions

E II'I—[I lllelTIWI—lI—ITrfii—l1‘lllllj

e I
it
E

E54
3%
U

0 l_l_l_l|llllllllllllllllllllllliLlllJ_
0 0.] 0.2 0.3 0.4 0.5 0.6 0.?
Electron energy (Rydberg)

Figures.”
Collision strength for the first transition in Fe VI GUI-"m -— ‘F312) from the Iron Project CC
R-matrix calculation. The symbols 0 and x indicate previous results, neglecting resonances
(from Chen and Pradhan 1999. Am, 136. 395).

At high densities. the population distribution is dominated by collisions and the

principle of detailed balance requires that the excitation rate from a lower state 1
to an upper state 2 is exactly balanced by the die-excitation rate from 2 to 1:

fl2n¢C2l =nln,Cl2. (5.122)

Since the population ratio of the two states is given by the Boltzmann equation. the
collisional excitation and de—eitcimtion rates are therefore related by

£1; = Sig—Emu. (5.123)

Cu 31
Assuming a two-level system and negligible background radiation (so that the
stimulated terms can be omitted). we have from the equation of statistical equilibrium

"2(A2l + ”ECZI) = nlnecu, (5.1.24)

 5.12 Collisionat'ly Ercired Lines 155

and the solution is

22 ___ neCIZ l
(5.125)
"1 A21 1+?

At high densities. this solution reverts to the Boltzmann distribution.

The critietnr density (11:) can be defined as the density at which the collisional
de-excitation rate equals the radiative de-excitation rate:

= Ej<i AU
"c (5.126)
Ens.- Cu"
At densities higher than no collisional de-excitation becomes significant. and the
forbidden lines will be relatively weaker as the density increases.
in photodissociation regions. fine-structure lines with different critical densities
(e.g., [O I] and [C II], Table 5.11) can be used to derive density. Lines with similar
critical densities (e.g.. 63- and l46-um lines ofO I) can be used as temperature probes.

Table 5.11
Spontaneous decay rates and critical densities for seven] forbidden lines

Species Transition Mum] Ms 1) "ACID—3)“

Optical forbidden lines

N' '01 JP; 0.65334 3.0 x to 3 7.0 x 105

0+ 20”: J5”, 0.37233 16 x 10-5 3.1 x 103
293;: J33” 0.37260 1.3 x 10" 1.6 1: :0I
o++ '02 JP, 0.50069 2.0 x 10-2 3.6 x 10*
Infrared fine-structure lines

c” 3P. Jro 609.|35 7.93 x 10-3 1.7 x 102

3P2 —3P. 370.415 2.63 x 10—1 7.1 x 102
c+ 1133,2 JP”, 157.741 2.36 x 10-6 3.0 x 103
0° 33,—310, 63.134 3.95 x 10-5 9.3 x In5
311, —31P. 145.526 1.70 x 10-5 1.5 x 105
0++ 3P1 JP; 51.3 9.3 )r. 10-5 3.3 x 103
39. Jpn 33.4 2.6 x 10-3 1.7 x 101
31+ “rm JP.” 34.315 2.13 x 10 -" 3.4 x105
'Cllwlated for T, = 10‘ K.
Adapted from Osterhuek 1989. Amphysicr ofGt-mou: Nth-Ila: andAcn've Galactic Nuclei. and Watson I935.
Phyrit'a Seripra. T] l. 33.
156 Line Radiation from Atoms and fans

5.12.1 The 21-cm H I Line

Since neutral H has two hyperfine states (Section 5.4.1). it can be well aPPTOli~
mated by a two-level atom. The small value of the spontaneous emission caefiiciem
(A = 2.369 x 10"5 5") implies a radiative lifetime (l/Aij) ofthe upper state ofap.
proximately 10 million years and a critical density of ~ [0‘5 cm‘a. From eqs. 5.125
and 5.123, we see that the relative populations of these two states are determined by
collisions and are given by the Boltzmann equation. Since the separation betwacn
the upper (parallel nuclear spin) and lower (antiparallel nuclear spin) state is only
5.9 x 10‘6 eV and much smaller than H"... the exponential term in the Boltzmann
equation can be neglected and the ratio of the population of the upper to lower stat:
is just the respective statistical weights (2F + I. or 3 to 1).
From eqs. 5.45 and 2.38, the absorption coefficient is

2
a. __ (1 _. e 4W!” ) .71 ..
m'cffla... (5.127)

Since the condition of hv/kT << 1 is always true for the Zl-crn line (It u/kT = 0.001
even at the low temperature of 10 K).

au-exm) by we2

= [1.05 x 10-ls cm2 5"] (591:5) av. (5.123)

in the diffuse ISM. the optical depth of the line at a specific velocity (u),

r. = f n,-(H)(v. T)a.,(7‘) as. (5.129)

is generally small. Under Optically thin conditions. the intensity of the 2l-cm line
is proportional to the optical depth. The fact that a” is inversely proportional to T.
suggests that H 1 absorption in the Galaxy is dominated by cold gas.
The solution to the equation of transfer for a plane-parallel slab of material with
a uniform source function is given by eq. 2.79:

1,, =-. Inge—W + 5,,(1 — e'r"). (5.130)

where 155 is the intensity of the background continuum radiation. Substituting

eq. 2.38 into eq. 5.13. we can express the source function in terms of the excitation
temperature as
 5. l2 Cow's-tom")! Excited Lines 157

S _2hv3 1 (5.13!)
V- 2 In: '
c em-l
If we use the concept of brightness temperature (Tb, eq. 3.10). eq. 5. ISO becomes

1 e" l — e"
ehum, _ 1' (5-132)
rah/“To _ | _ ehvlkTaa . 1
At low frequencies where the Rayleigh—Jeans approximation applies.

Tb — Tao = (T; - Tact)“ - e"). (5.133)

Assuming Tb » T36 and T; >> T30. we have

flu in2

Since n,/n,- =3andnH=4nJ-.

hu 1:22
Tb ..t (:1?) (El?) ffidufnflds. (5.135)

Integrating over frequency, we have

fTbha) (11.1: (E) (32—) fjifnudsfoudv. (5.l36)

4k met:

The column density of atomic hydrogen can therefore be derived from the integrated
strength of the Zl-cm line:

41: mec l
fnflds— (R) (E?) f f T5001,”

=185x10'4cm 2 f Tb(v)du. (5.137)

Since the tempemure of the H I gas in the ISM is generally low, the intrinsic
width of the H 1 line is narrow. With heterodyne techniques, the frequency of the line
can be measured to a very high degree of accuracy, giving a precise measunnent of
the velocity and velocity di5persion of the gas. The 2l-cm line therefore represents a
powerful tool for the study of galaxy dynamics.
When observed against a radio continuum source. the H 1 line can be seen in
absorption. The strong H 1 absorption lines toward certain directions in the Galaxy
correspond to the presence of cold clouds.
ISB line Radiation from Atom: and tons

5.12.2 Forbidden Lines of Metals

Due to the low metal abundances and the small transition rates, the collisionnuy
excited lines are generally optically thin. The line intensity is directly,r PI'UPOl‘tiona]
to the line emissivity. which is given by eq. 5.11. As an example. the [011] chum“
M3726l3728 A can be considered as a pair of two-level atom systems because of the
small energy difference of the upper states 203,; and 205,; (Fig. 5.7).
Assuming E; = 53. v3, = v2]. and no transitions between levels 3 and 2, we find
that the intensity ratio of the two lines is

10125 A) _ nJAJ.
1(3723 A) nzazt
n C
= 9s
C
ltflu
5:211
. (5.133)
I2 1+ .43,

At low densities (neCzl << A2. and n,C3. << A31). we have

it! = Eu
’2: C12
9| 3
= —-‘—, (5.139)
91.2
which implies that every collisional excitation is followed by a line emission. Using
eq. S.l l9. we have

_=—.—=—. (5.140)

At high densities. eq. 5.138 gives

L]; =__ EACH/1421

’21 CI: Car/Ail
= 831431
82411
—4
= (3) M. = 3.3. (5.141)
3 3.6 x 10-5
which is consistent with the expectation that the population distribution should obey
the Boltzmann distribution. and the ratio of the populations of the two upper states Is
given by the ratio of their statistical weights.
 5. I2 Coilis'r'onally Excited Lines 159

31

23 2] l
3063
5755

4959
4931
65-48
27
JP,
JP:
51.3w: I
In pm
lpl
i
8?.4 pm 2t? um
3P0 3pa

0“ N4-

Figure 5.23
The ground-state multiplet of 0'H and N“. The magnetic dipole '01 — 3P” transitions of {0 III] at
1.4959 and 15001 A are among the brightest forbidden lines in the ISM. Also shown are the infrared
fine-moire lines in 39 (Section 5.3).

Therefore. the very different behavior of the line ratios at different density
regimes allows the [0 II] doublet and other similar ions with outer electron configu-
ration np3 (e.g.. [S II] 1.61 [6.6731 A) to be used as density probes of the nebula.
Another set of forbidden lines that is useful for nebular diagnostics are the
'So — 'D; — 3PM; transitions of ions with up2 electron configuration (e.g.. [0 III]
and [N [I]; see Fig. 5.23).
in the low-density limit. every collisional excitation will result in the emissiou
of a photon. and the upper states can be populated only by collisional excitation from
the ground state. The equations of statistical equilibrium are

"21421 = "Ineciz
"30‘s: + A32) = "IntCBI (5.142)
160 Line Radiation from Atoms and Ian:

where the levels I. 2. and 3 correspond to the P. D, and 5' states. respectively, The
solution to eq. 5.142 is

0
"a 13 A21
'— = ———_- 5J4
"2 12 511+ 3:12 ( 3)

The intensity ratio of the 4363-11 to the sum of the 5001-13. and 4959-A lines is
[(4363 A) = n 3 u 32 A 32' (5.144)
1(5007 A + 4959 A) flzvzlAu
Substituting eqs. 5. I21 and 5. [43 into eq. 5. I44, we have

1 4363151
#1, 9 _
= J6 v A
55:111. (.12.) _32__ (5.145)
((5007 A + 4959 A) 912 11:. A31+ A32
With E32 = 2.84 CV. A32 = 1.3 S_|. A31: 0.2218-‘1. “'3 = 0.23, and Q” =
2.17, we have

#3533“)— = 0.132 x [329901; (5.145)

1 (5007 A + 4959 A)
The measurement of this line ratio therefore can serve as a probe to the electron
temperature. At densities close to or higher than the critical density (Table 5.11).
collisional ale—excitation terms have to be included in eq. 5.142 and the line ratio will
be slightly different from that given in eq. 5. [46.

5.13 Resonance Fluorescence

While the low-lying states of metals can be excited collisionally, the high excitation
potential states of metals have low populations due to the slowness of the recom-
binaIiOn process. In fact. pennitted recombination lines from high-level states are
generally weak except for H and He. Therefore. the observations of strong permit-
ted Iines from O++ in the near UV were not expected. The excitation mechanism
was identified by l. S. Bowen as due to a wavelength coincidence between the Lya
(1303.730 A) line of He 11 and the 21;2 3P2 — 3d 3?; (2603.799 A) transition of 0
III, and this process is now referred to as Bower: fluorescence. Subsequent cascades
to the 2322p3p (351 and 3012.1) states and further cascades to the 2522,1135 3P2”
give rise to the strong visible lines observed (Fig. 5.24).
Charge transfer (see Section 4. ID) of 03+ in collision with [-1 can populate the
excited states of 02+, in particular the 2p3p 3D and 2p3p 35 states. which contribute
to the Bowen cascade. The efficiency of the Bowen fluorescence process is measured
by the fraction of all the He II Lya photons created by recombination that are converted
to photons in 0 III transitions, excluding the 2p3p —- 2p2 transitions. The typical
observed efficiencies are ~ 0.1 — 0.3.
 5. 1'4 Recombination Lines ofMetals 16]

I 0 [I]
H: II I
I
__._—- 2sz : 2p3d 3191
I
I
I 3444 3429
l 2820 3:33
I 2 J
I 2331 ——I 2p3p P
I 303.62 2309 _—o
I
l J
303.78 I 293” S
I 2
I I 2p3p’D
: 303.30 _ o

1 ———2
| -—'—————"' | 21:35 ’P
I o
I
I 2
__.——l—-—-—7.t'2$ I ——- 1 2pm:
' o
I
FlgttreSJ-‘t
A schematic partial energy diagram of OH illustrating the Bowen fluorescence. Not all levels or
transitions are shown.

5.14 Recombination Lines of Metals

In addition to resonance fluorescence. optical permitted lines of metals, although

weak, have been observed in photoionized regions. Recombination lines of 0'”
were first observed in the OriOn nebula. and recombination lines of C+. C”. and
C+++ in the visible region can also be observed. Since the strengths of recombination
lines are less sensitive to electron temperature than collisionally excited lines. there
are advantages of using recombination lines to determine the abundances of heavy
elements. For example. the N w 5330 — 6h3H" A4606 A and the 01V 5320 — shim
M632 A lines have been used to deduce the abundance of N4+ and 05*. respectively.
When an electron makes a transition fmm one electronic state to another. the line
is “pennitted” if the selection rules of the H coupling are satisfied (e.g., A8 = :1:1.
Section 5.1). For example. singly ionized oxygen with 7 electrons can be in the
following electronic states: 13:22:22}:3 (ground state). 2p5. 2.5221324f. 2522p23p.
2p44f. and 2p43,5? (all odd parity states). or 252,04. 2322,9235. 2:22pm. and 2MM
(all even parity states). and so on. Permitted transitions between these states can occur
as a result of recombination. Examples of some of the strongest optical recombination
lines of 0+ are listed in Table 5.12. Lines in the first group in Table 5.12 from the
311;4 D" — 3s‘P multiplet are the strongest among the recombination lines of 0 II.
Table 5.1.2
Optical mombinaticm lines of 0+

Wavelength (A) Transition

3p — 11'

4630.06 3,1"I 173,2 — 111‘?”-z

4641.02 3pm”, — 3dr”,
4649.14 Jp‘om - 344725,,
4650.04 3134171,, - 31‘?”1
4661.63 sp‘Dm - 39419,,2
4673.74 3pm”; - 31493,,
4676.24 3640”, - 36113,,
4317.14 Jp‘rm — 36‘1"”2
4319.63 3p‘Pm — 3MP,”
4325.16 317‘ Pm — 35‘1“!”
4345.56 311421.,2 — 3147:,”
4349.43 3114.95,, — 3611,”
4366.09 3114193.,2 — ss‘rm
4414.90 371217,,2 — 311?,”
4416.97 317203;; — 31:119.,2
4452.37 3,0203}: — 31115,,
341 - 3p

4069.09 30413,, — 3114173,,

4072.16 344 Fm — 3p‘D5fl
4075.06 M‘Fm — 31mm
4070.04 30‘ 1-3,, — Jp‘om
4005.11 30‘an — 3.6417,,2
4092.94 id‘Fm — 3p‘ 17,,1
4094.14 34‘1“,” — 3p‘D5n
300219 344171,, — 3,6401”.2
4132.00 344173,, -3p‘Pm
4153.30 34415,, - 3114.93,,
415653 ad‘Pm - 3p‘Pm
4169.22 34419,” - 3p‘P5/2
4110.79 3441).” — 3pm,,2
4119.22 7.7114174,z — 3,6413”:
4120.20 3441),” — 3117410,”
4369.20 M10312 — apzom

Soul-u: [in at al. l995. ”NR/IS. 271. 369.

 5J6 Determination of Nebular Density and Temperature by Diagnostic Diagram 163

5 15 Statistical Equilibrium and Population Distribution

Bound—bound transitions in an atom can take place as a result of Spontaneous emis-
sion. absorption. stimulated emission. and collisional excitation/devexcitation. For a
two-level atom in a steady state, the rate of upward transitions must balance the rate
of downward transitions. Taking into consideration radiative rates (spontaneous and
stimulated emission. absorption) and collisional excitation (n,CJ-l) and de-excitation
(o‘cij) rates, we can write the equation of statistical equilibrium as

"1' (Biijii + "rCh-J =nt- (Bi-iii,- + Aij + n,C,-,-). (5.147)

where 1.” = if,- is the background radiation field given by eq. 5.2. Generalizing to
a multistate atom. the outgoing rate from state j must balance the incoming rate to
state j:

2 Air] = Z "t (act,- + Hui”) + 2 wt,”- (5.143)

”t [Z (Bikjt'i + "ccik) + k<j
I it k>j

This system of linear equations of statistical equilibrium can be solved together with
the condition of conservation of particles

Zn,- = N. (5.149)
t
to obtain the population of each state ifall the radiative and collisional rates are known.
For example, the population distribution of the [0 III] multiplet (Fig. 5.23) can
be solved by a set of five simultaneous linear equations. From eq. 5.] l, the emission
coefficients (and therefore the strengths of the lines) can be calculated, and the results
are plotted in Figure 5.25. We can see that the strengths of the optical collisionally
excited lines decrease rapidly with temperature and become neglible below [000 K.
whereas the infrared fine-structure lines remain strong until about 100 K.

5.16 Determination of Nebular Density and Temperature by

Diagnostic Diagrams

In the previous section, we saw the example that the ratio [(4363 Ayrt4959 A +
5007 tat) gives the electron temperature for [0 m]. whereas [(3726 it)il(3729 A)
gives the electron density for [O n]. a different ionization stage. However. [0 III] and
[0 u] may originate from different emitting regions and the temperature and density
measurements may not correspond to the same region.
For a p3 configuration as in [s It]. the line intensity ratio 1(6717 tit/«6730 A),
together with the line ratios moss A + 4076 A)tr(671't A + 6730 it). gives both
T, and n, in the same radiating volume for the same ion. Similar line ratios can
be obtained from other p3 ions such as [O n], [Ne w]. [C1 in], and [Ar Iv]. Willi
164 Line Radiationfmm Alarm and [arts

fillllll‘l] r llllllil— I

[0 Ill] 1500'!
10-20 ‘
6
[0m] 52mm
--21 __.. ------------- 7
m x" "'" -4
1”
a" I _,_. ------------------- 5
+
w 10*22 ’ ”
,-——"
5 m”. ,_.. ------------------ 6
310‘” .. :I')‘-7..'. _______ LogNe(crn‘3)
R --.’_1. ..............

33 I’ """"""""""""""
3W 10-“ ........................
----------------
........... 01114649
'0‘” ........... _

Hfi14649
lo 26

l0_17_LL t tttttttl l._l_lllllll LI

101 IO3 10"
TAK)

Figure 5.25
The dependence of the emission coefficients of the optical recombination lines H15 and O II
14649. and the collisionally excited lines [0 III] 1500'! and 52 pm. as functions of electron
temperature. The optical recombination lines are essentially independent of electron density.
For the collisionally excited lines. the dependencies on several densities are shown (from Uu,
X.-W. 2005. in Planetary Nebulae beyond the Milky Way. eds. L. Stanghellini and .I. Walsh).

a combination of different transitions and ions. the values of T, and u, should be

confined to a narrow region (see Fig. 5.26). The fact that the curves do not intersect
at a single point suggests that the temperature and density distributions may not be
homogeneous.

5.17 Atomic Parameters

Recent advances in computing power have made possible the calculation of photm'on-
ization cross sections (av). recombination coefficients (er). transition probabilities
(Aij 0|' f1:). and collision strengths (9n) for electron excitation of complex atoms
and ions. Efforts undertaken in the Opacity and Iron projects have resulted in data-
bases of accurate atomic data and stellar opacities. The Opacity project has prOVided
 5. i8 Abundance Determination by Absorption Spectroscopy I65

Diagnostic diagram for IC 4997

I I | | I r I I I I I I II I I I | I | I' I |
3011]) [1—1 I I I : I_I bi I‘ i i.I | I I I I I I I I I | I

l' l i i I i '
' [0 '1 i ' I ' fl‘
25,000 - (2) I 3%" i i \
' I '. 1 \[0 m1". .
- I t I 4
5-” ' \ ': i \t) l ‘
3" ‘ \ '. i, I \‘ —4
‘
“'- 20.000 L [N H] t | \ :_ t. I\ 1
5E - t1) ' ' t8 u] \ 1 \ \ ._\ -
- i 1‘ [CL Iv] '
E
s
'
- I
- ' '.
\
§ 15.000 — [Ar 1 i \ -
- -
I- IV .
g L (11) 5 \‘.\‘~.., I
' i ‘ [o m]
to,ooo-———-—'f*"" cg) ii
- i '-.___
[0 m] t'

_
I 6)

I
i

'\
. -..
H. _____
---.1
m l l_LL':l_Ll l i l l I l i"‘I_I_I JJ 1 l_|_.|_ t_i_I"i*-I I I I M_
3.5 4 4.5 5 5.5 6 6.5 7 7.5 8
Electron density. log N,

Figure 5.26
The electron density temperature diaglam for IC 4997 using difl'erenl collisionally excited lines as
diagnostics. The fact that these curves do not intersect over a small area suggests that they arise frorn
regions ofdifferent temperature and densities (from Hyung at at. l994, ApJS. 93. 465).

phOIoionization cross sections for ~ 200 ions with Z =l-l4. 16. [8. 20. and 26. the
energy levels and transition probabilities for ten million transitions. and Rosseland
mean opacities. The Iron project has computed collisional data for the iron-peak el-
ements in different ionization stages. These detailed calculations have revealed the
extensive resonance structures in 9(E) (Fig. 5.21), resulting in larger values of the
collisional excitation rates CJ.,(T,) when averaged over the Maxwellian distribution
(eq. 5.120).

5.18 Abundance Determination by Absorption Spectroscopy

The gas-phase abundance of atoms and molecules in the ISM can be detennined by
measuring the Strength of absomtjon lines arising from diffuse interstellar clouds
166 Line Radiation from Atoms and Ions

against the background of bright O and B stars. Since most ground-based transi-
Lions of atoms and molecules occur in the ultraviolet, this requires observations from
above the Earth's atmosphere. Early studies began with sounding rockets. followed by
the Copernicus and IUE satellites. Later. high-resolution UV spectroscopy became,
possible with the HST Goddard High-Resolution Spectrograph (GHRS) and Space
Telescope Imaging Spectrograph (STIS) instruments and the FUSE satellite. Obser.
vations from space allow access to abundant elements such as C, N. 0. Mg, 81, and Fe
in a number of ionization states. In contrast, elements observable in the Optical from
the ground are limited to Li I. Na l, Ca 1. Ca n. K t. Fe t. and Ti II.
The colurrui density of the gas can be derived from the equivalent width through
an analysis ofthe curve ofgrowth, and can be obtained from eq. 5.83 or 5.92 depending
on whether the line is optically thin or totally saturated. The usual notation For the
abundance ofelement X with respect to hydrogen is (Xf H l = N (X )l N (H). Where N
is the column density. The notation [X[H] is used to refer to the logarithmic abundance
relative to the solar value:

[X/H] = log(X/H) 7- log(X/H)O (5.150)

If an element is found to be heavily depleted in the gas phase compared to its solar
value. the missing abundance is likely to have condensed into grains (Chapter 10).
The amount of an element incorporated into grains can be inferred from its observed
gas-phase abundance:

(Jr/H)... = (Jr/mo — (Jr/H)... (5.151)

where the subscripts d and 3 refer to dust and gas, respectively.

5.19 Abundance Determination in Emission Nebulae

While the determination of elemental abundance by absorption spectroscopy is lim-

ited to lines of sight From bright ultraviolet sources, emission spectroscopy canbeused
whenever emission lines are observed. However, the analysis is more complicated be-
cause the strength of the line is dependent on excitation conditions. For coltisionally
excited lines, the emission-line strength is controlled by the electron temperature and
density. These parameters can be derived through an analysis of line ratios. as de-
scribed in Section 5.12. For example. electron temperatures can be derived from the
ratios of [0 III] (4959 A + 5007 iii/4363 A and [N it] (6584 A + 6548 iii/5755 A; and
electron densities can be derived from the ratios of [8 II] 6717 Atom A. [Ar w] 471 l
A14740 A, and [Cl iii] 55!? 115537 A. The abundances of various ions relative to H
are then obtained by solving the statistical equilibrium equation using recombination
or collisional excitation models. The total elemental abundances are then obtained by
applying ionization correction factors. which correct for abundances of unobserved
ions. The uncertainties inherent in the last step can be improved by including lines
in the ultraviolet and infrared. For example. by combining optical and UV lines. one
can observe several ionization stages of an element. For example. C II 4267. C till
1909. and c W 1550 give abundances of c+. C2+, and (33+. respectively. and [0 II]
 5.20 Summary 167

3728. [o m] 5007, and o w] 1400 and 26 ,um give abundances of 0+, 01+, and 0“.
respectively.
As we have seen in Section 5.16. the forbidden-line ratios do not necessarily
converge to a single point to give a unique solution for T, and n,. The fluctuations of
either parameter in the nebula can have profound effects on abundance determinations.
For example. [0 III] is excited by collisions whereas Hfi is excited by recombination.
Since these two processes depend on T, in different ways, the O++ to H+ abundance
ratio determined from the [0 III] to Hfl line ratio can be in serious error.
Although collisional excitation is several orders of magnitude more efficient
than recombination at high temperamres (1", ~ 104 K), the collisional excitation rate
(eq. 5.121) and therefore the emissivitiec of UV and optical collsionally excited lines
decrease exponentially with decreasing temperature. In contrast, the recombination
rate (eq. 4.42) and emissivities of optical recombination lines increase with decreasing
temperature. For example, when T, drops below ~ 3000 K. the strength of the
recombination line 0 n A4649 becomes stronger than the usually prominent nebular
collisionally excited [0 III] AA4959. 5007 lines (Fig. 5.25). While fine-structure lines
arising from low-lying states such as the [0 III] 52- and BB-um lines are less affected
by temperature. they nevertheless become very weak at low temperatures of a few
hundred degrees. The very different dependencies of collisionally excited lines and
recombination lines on temperature suggest that they represent probes of high and
low temperature regions, respectively. The abundances determined from these two
kinds of lines may therefore reflect those of different temperature regions.
Sometimes an emission line can have more than one source of excitation. The
standard method of abundance analysis for He is to use the effective recombination
coefficients. However, the lowest triplet level (ls 3.S‘) and the first excited state (25 IS)
of He I (Fig. 4.2) are metastable, and collisional excitation from these two levels can
excite the observed He I "recombination" lines in dense nebulae. For example, the He I
110830 A line is strongly enhanced by collisional excitation from the is 3S state. A
proper analysis of the recumbination line strengths of He I therefore needs to include
the contribution of collisional excitation.
The abundance of certain heavy element ions can be derived from either colli-
sionally excited lines or recombination lines. The most commonly used recombination
lines in the optical include c u A4267 A. N n A4041 A. o u 2.4089 A. Mg 1: AMBIA.
and Ne II A4392 A (Section 5. l4). However, the elemental abundances derived by the
two methods do not always agree and the origin of this discrepancy is still very much
a mystery.
Another major uncertainty in abundance determination is the degree of depletion
of atoms in grains. If the dust-to-gas ratio (by mass) is low. then dust depletion will
introduce only a small error in the abundance determinations.

5.20 Summary
Electronic transitions of atoms and ions can occur in the X-ray, UV. visible, infrared,
submm. and radio parts of the spectrum. While recombination lines of H and He are
usually the strongest lines observed, collisionally excited. permitted lines of metals
[68 Line Radiation from Atoms and ions

are new commonly detected in the UV. The low-density conditions of the ISM imply
very low collisional de-excitation rates. which allow many forbidden msifions to
occur. These transitions can take place between finestntcture and hyperfine states,
making the ISM a unique laboratory for the study of metastable states of atoms and
ions.
Emission-line spectroscopy of atoms and ions remains the powerful diam-103m:
tool for the study of the ISM. Through the measurements of ratios of line strengths,
we can determine the environmental conditions (temperature and density) to high
degrees: ofaccuracy. From the absolute line strengths. we can determine the abundant-z
of elements and isotopic ratios. From the line profiles, we can also learn about
the kinematic structure of interstellar clouds. By observing the same element in
different ionization stages, we can infer the radiation environment if these elements
are photoionized.
Line radiation from atoms and ions plays an important role in the energy balm
of the ISM. Collisional excitation of the low energy States of neutral atoms and ions
of common metals such as C and 0 removes kinetic energy from their surrounding
medium. and line transitions from these states are powerful agents of cooling of
interstellar clouds.

Further Reading

Aller. L. H. I963, Astrophysics: 11n- Atmospheres ofSun and Stars. Ronald Press.
Osterbroclt. D. E. [939. Astrophysics of Gaseous Nebulae and Active Galactic Nuclei.
University Science Books.
Bemalh. P. I995. Spectra ofAtoms and Molecules. Oniord University PteSs.
Rybikj. G. B. and Lightman. A. P. 1979. Radiative Processes in Astrophysics. Wiley-
lnterscience.

Resource Materials

National Institute of Standards and Technology (NIST) atomic spectra database:

http:/twwwphysics.nist.gov/cgifibiniAtDatalmanflasd.

Exercises

l. The first excited state of hydrogen is made up of a number of degenerate states.

0 Write down these states in spectroscopic notation (in 7-!Mid).

- What are the degrees of degeneracy in each of these states?
0 Which of these states have pennitted electric-dipole transitions to the ground
state?
 Exercises 169

- If each of these states has 1110 the population of the ground state. calculate the
source function of the permitted transitions.

2. Using the rules of angular momentum addition, show that all the suites shown in
Figs. 5.? and 5.23 can be produced under the p3 and p2 electron configurations.
respectively. Show also that the relative energies of the states obey Hund‘s rule.
Ne3+ has a pair of P and D doublets with a quartet of transitions at 4715. 47l5.
4724, and 4726 A as a result of spin—orbit coupling. (a) Designate these four levels in
spectroscopic notation. (b) Which of the four transitions are permitted electric-dipole
transitions? (c) The strongest line of this multiplet is likely to be between states of
the largest statistical weights. If the strongest of the four lines has a relative strength
of 0.6. calculate the relative strengths of the other lines in this quartet.
:5

Assuming gum) = I, calculate all recombination coefficients up to n = 10 of the H

atom for T, = 10‘ K using eqs. 4.40 and 4.41. Also calculate the total recombination
coefficients under Case A and Case B by ignoring all states above n = 10. Techniques
required: change of variables and numerical integration.
. An interstellar cloud has a density of to H per cm3, a temperature of 10 K, and a
radius of 1 pc. If the line profile can be approximated by a square profile of 1 km s '
wide, what is the integrated optical depth of the 21-cm line?
. Find the ratios of line intensities for a three-level atom. taking into account transitions
between all three levels but ignoring the stimulated radiation (Br'j and Bj, terms).
Compare these results with the approximate solutions in Section 5.12.
Plot the line ratios 132/12, as a function of electron density for [On] for T, = 10“
K. Discuss the values of this line ratio at high and low densities and estimate the value
of the critical density. The energy levels. collisional cross sections. and the Einstein
A coefficients are given in Table 5.13.
. The l2.8-u.m line is a strong emission line in the infrared spectrum of emission
nebulae. This line is identified as the 2P, ,2 (upper) to 2P3” (lower) transition of singly
ionized Ne. Assuming that this line is collisionally excited. calculate

- the collisional excitation and de-excitation rates of this transition

° the ratio of Ne ‘ ions in the upper and lower states

at temperature T, = [04 K and density n, = 10.000 cm‘3. The collisional strength

(9) of this line is 0.37 and the spontaneous decay rate is 3.6 x IO‘3 5".
. Assuming gut") 2- l. by eq. 4.39, calculate all recombination coefficients up to
n = 10 of the H atom for r, = w" K using eqs. 4.39 and 4.41. Also calculate the
total recombination coefficients under Case A and Case B by ignoring all states above
in = l0.
. Using the expression for the somce function of bound—bound transition (eq. 5. I2) and
the equation of statistical equilibrium

”J- (ijJ—+CJ-,-)=ni (Alj+Brjj+Cij)' (ESJ)

ITO Line Radiation from Atom: and Ian:

Me 5.13
Radiative and collisional uansilion rates of 0+

i. j transition 11,-,- (151) (Ax,- 5") 9;.-

31 21°31: 453,; 2470.3 5.0 x 10'2 0.2704

117", «"53,2 2470.2 2.4 x 10-2 0.1352
21 203,2 4.9”, 3726.0 5.5 x 1073 0.5340
10m 453,-, 3720.0 4.0 x 10" 0.0010
32 2P:n JD,” 7329.6 9.4 x 10-2 0.2747
217,,2 J13”2 7319.9 1.1 x 10-' 0.7302
2193,, —2Dm 7330.7 5.0 x 10-2 0.4077
1.0”, 3.0,,2 7310.0 5.5 x 10-2 0.2951

Data from Ouethmcl. D. I989.A:1rophy:1c5 afGaum Nebulae anddcn've Galactic Nuclei. Universily Hm
Books. and Pradhan. AK. 1976. MNMS. 117. 3 ll‘.

show that

j+43
s = ————£. .
” 1+ A (E5 2)
where

c..
A = in — ("WT-1. (05.3)
I;
10. Give some examples of alomic lines mat can be used to infer the presence of high
temperatures as in the ISM.
11. Figure 5.13 shows that the fine-structure line of the rare element zinc is stronger than
Ihe lines of the mos! abundant element H. Why?
/fi
Continuum Radiation
in the Gas Phase

Several processes contribute to the gas-phase continuum emission in the ISM. In the
visible region. the main contributors are the free-bound (f-b) emissions from H and
He in the ionized gas. In the infrared. free—free (f—f) emissions become stronger
than the f-b emissions. and in the radio domain. the f—f process is the dominant
emission mechanism in H II regions and planetary nebulae. In Supernova remnants.
the dominant mechanism is synchrotron radiation due to the interaction of relativistic
electrons with magnetic fields. In the near ultraviolet, there is a continuum resulting
from the two-photon decay of the 225' level of H, a process that is not observable in
the laboratory environment.
Some of these continuum emission processes (f—b. f-f. electron scattering) are
the same physical processes that are responsible for die opacity in stars. While the b—f
processes remove light by photoionizing an atom. the reverse process (recombination)
leads to emission over a continuous frequency range. The absorption and emission
processes in f—f differ only in whether the electron gains or loses speed after an
encounter with an atom. H and He. with their high abundances. are mainly responsible
for the continuum emission processes. Unlike line emissions. heavy elements in the
gas phase have minimal contributions to continuum emissions in the ISM.

6.1 Free—Bound Continuum Radiation

The main contributor to the continuum radiation in the optical region in emission
nebulae is f—b radiation. Every time an electron of mass m, traveling at velocity v
reenmbines with a proton to form an atom at level n. a photon of energy

1
hu=§m¢u2+% (6.1)

is emitted. The recombination rate to level n from electrons in the velocity range from
u to u + do is

Fundy =npn,f(v. 1",)vcr,1 du. (6.2)

171
l72 Continuum Radiation in the Gas Phase

Assuming that the electrons obey the Maxwellian distribution, we can Obtain the
emission coefficient by melting use of eqs. 4.33. 6.1, and 4.39:

4n}, =th”,,
32
= E 33. e211 0.3.2, ; ’ renames”,
«I'm; 3J5 m3c3 ' 2x): 13/2 n3
n
= 2.16 x 104257123 g—lgrel'lvn'")’”‘ ergom‘3 s"I Hz“. (53)
n
8

The total emission coefficient, talcing into account recombination to all levels. is

CC
’3 H
47tju = 2.16 x 1042—13}; 2 %e“”fl'”””¢ erg em‘3 s'l Hz". (54)
f n |=.r|’

Since any f—b photon due to recombination to level n’ will have the minimum
of hunr, on: must be less than v. The emission coefficient for H at T, = 10‘ K is
shown in Figure 6. I. At 13646 A (Balmer limit), the f—b emission coefficient has a
discontinuity known as the Balmerjump:

I—
05 = log F . (6.5)

where l ' and l‘l' represent the continuum level at either side of 1);. The values of
1‘ and 1* can be calculated by taking the ratio of jIJ at u = v; for n’ = 2 and 3.
respectively. At T, = 10000 K, D, has a value of 1.36. Observationally, 03 has
been found to have values much less than 1.36. which could be due to the rise in the
continuum level by contribution from scattered light.

6.2 Two-Photon Radiation

The 223”; level of the hydrogen atom is metastable. Due to the spherically symmetric
nature of the initial and final wavefunctions. radiative transition to the ground state
125 will have at = 0 and Ant = 0 and is strictly forbidden (all multipole mtilflltfllIs
are zero). A radiative transition to the 221’ l.-'2 level has a very low probability and will
occur only once every 30 million years. The only way an electron can escape from
the 23 level is by photoionization or collisional transition to the 22?”; state. which
then quickly decays to the ground state by emitting a Lya photon.
 6.2 Two—Photon Radiation 173

10,000 7500 7500 5000 4275 3750 3300 30G]

T= 10,000 K

1:" rtHen)

a
is
U

E.”
0 .-
E 10'” ' l \\ l
.2 ‘. l
g ytnc I) 5
3U \‘
'
i

5
.5
NH!) x ‘\‘
.
E

r094) i

I_ I l l I r
3.0 4.0 5.0 6.0 7.0 3.0 9.0 10.0
Frequency (10" Hz)

Figure 6.1
Free—bound continuum emission coefficient (41mg! .01],) for H 1 (dashed line). He 1. and He u
at l0,000 K. The curve labelled 1424) is the two-photon continuum from H (from Brown and
Mathews 1970. ApJ, 160. 939).

In low-density environments such as those found in planetary nebulae. an electron

in the 2251;; level can jump to a vinual p state. which lies between it = l and n = 2
levels. The electron then jumps from this virtual state tothe ground state. in the process
emitting two photons with total frequency v] + v2 -: v.4“. Such virtual states are
possible as long as its lifetime (time between having come from 2: and taking off
to Is) is small enough to be allowed by the uncertainty principle. Since this virtual p
state can occur anywhere between it = 1 and n = 2. continuum emission longward of
Lya will result. The emission coefficient of the two-photon (2-)!) process is given by

h (6.6)
4runny) =nzzs" P My).
ya
114 Continuum Radiation in the Gas Phase

where y = v/ v1”, and A (y) dy is the probability for emitting a photon in the imerval
dy = do] 11,“. The maximum probability of the Z-y emission corresponds to the Case
when each photon has the same energy (y =-— l/2. or hv = [Iowa/2 = 5.1 eV),
The Function A(y) can be approximated by the following expression:

11(y)=202.05'l
x [m — y) x (1-{4yu— 301““) + oastya — 301'” x [4y(1— mm]
(6.7)
and the total radiative probability for the 25‘ —> Is transition is

l
14.225195 =10- AO’) dy

= 3.2249 s“. (5,3)

Although the photon number distribution peaks at y = 1/2. the emission coef—
ficient j.J o: yA(y). Differentiating yAty) and setting the result to zero. we find a
maximum at y = 0.7526. The maximum of j” therefore occurs at ~ 0.751)”... For
optically thin emission. the flux distribution (Fv) peaks at A. ~ l6l5 A. Using eqs. 6.6
and 6.7. we can obtain the emission coefficient and the result is plotted in Figure 6.2.
Under Case B conditions. Lye: is trapped between the 22? and IIS states; every
emission out of 2P is followed by an upward transition by stimulated absorption. The
principal way out of the 21’ state is through a collisional transition to 223. followed
by a 2-y emiSSion. In this case. the population of the 223 state is maintained by a
balance between recombination and Zr radiation:

"pnela513(Te) + ”122,412”: "225A225_125. (6.9)

where (1’02) is the total rate of populating a state by direct recombination or by

recombinations to higher states followed by cascade to that state. Under Case A. the
21’ state can depopulate via Lyar emission. and the 23 population is given by

npn‘aézs =n225A223J25‘ (6-10)

At T, = 104 K. a’ s and at; P have values of therefore occurs at 0.833 x 10'” and
1.74 x 10"13 cm3 s' . respectively. Since all cascades will end upin either 225 W22?
states, the sum ofo;s and oh, must be equal to on (Section 4.5). The level population
n22; obtained from these values using eqs. 6.9 or 6.10 can then be substituted into
eq. 6.6 to calculate the spectrum of 2-}! emission under Case A or Case B conditions-

A similar process also occurs in the singlet state (2 ' So) of neutral He (Fig. 4.2) and
the 2181,; state of ionized He. Observationally. the 2-)! continuum from He+ is less
 6. 2 Eva-Photon Radiation 175

1.0 I I I I I I I I I I I I I I l

1
I
0.9
I
I
I

llIllII
0.3
41rjvln3(10"-" erg sec ‘ Hz“)

I
I

0.7
I
I

0.6
I
I

0.5

IlIlII
I
I

0.4
I
I

0.3
I
I

0.2
I
I

0.I
I

0.0 . I l l . l l l . I I I . I 1

IZW ”W I400 ISW I6“) ”00 1800 I900 2000

Wavelength (A)

Figure 6.2
“no-photon continuum emission coefiicient (4njv/n225) for H as a function of wavelength.
The SI'Klfl Wavelength limit for the emission is Am at [216 A.

important than H because it peaks much further in the ultraviolet. and the abundance
of ionized He to H is low. The emission probability My) for a hydrogenic ion with
nuclear charge Z can also be approximated by eq. 6.7 with the first cornstant replaced
by 260?, 112.9202 5-1. The total transition probability is

A22l" = 822492651
RH
5—1. (6.11)

Figure 6.3 showsasimulated specuum (near UV to near infrared) ofan ionization-

bounded nebula. The photosplteric continuum (assumed to be a blackbody) of the
central star is also plotted. We can see that the stellar Lyman continuum is completely
absorbed by the nebula and its fluxes are redistributed to the gas component in the
form of emission lines and nebular continuum. The Balmer. Paschen, and so on.jumps
of the f—b continuum can clearly be seen. and the 2-}! continuum can be seen in the
near UV. The emission spectrum beyond the Lyman limit is made up of nebular lines
from higher ionization states of metals.
176 Continuum Radiation in the Gas Phase

r I I I r r I I I I I I I I l l 1 I l I

104

[0‘9

A
i
I l

E " 't. I

E m—lflI I r i I
13 i .. I i I
2 [I I | I I
I. II ! ' I
[0 l:
If )
II ilr. ' I‘
I
i

l “
i 1.
1042 ' I In

I I I J l I l 1 l l _I__L _i_ _l_l J

10'I 10° l01

Wavelength A (pm)

Flguredj
The spectrum of an ionization-bounded nebula calculated with the CLOUDY photoionization code
of Gary Ferland. The nebular continuum is primarily due tof—b emission. with contribution from the
two-photon emission in the UV. All the energy in the emission lines (primarily recombination lines
of H and He and forbidden lines of metals) is extracted from the Lyman continuum of the central star.
which spectrum is shown by the blackbody curve (figure from K. Volk).

6.3 Free—Free Continuum Emission

Whenever an electron passes near an ion. it is accelerated and emits a radiation pulse.
Since each free electron has a different energy and passes the ion at different distances.
this results in a continuum radiation called thermal bremsstrahlung or free-fine (Jr-f)
 6.3 Free—Fae Continuum Emission I77

radiation. The emission coefficient for f—f emission is given by

on

ju=f f(v)w(v)dv. (6.12)

x

where f,(v) is the velocity distribution of the electrons. and

Sire"
100:) = ugh-223w, u) (6.13)
3x51911131:

is the power radiated in unit volume per solid angle per unit frquency (in units of
erg cm'3 s'1 ster—1 Hz" '). Z is the nuclear charge. and 30:. v) is thef—f Gaunt factor.
The lower limit of the integral in eq. 6.12,

”2
x = (27:2) , (6.14)
E

is set by the fact that radiation at frequency u can arise only from interactions with
initial kinetic energy %m,v2 greater than hv. Assuming a Maxwellian distribution for
f(v) (eq. 2.37), the emission coefficient at temperature To is then

31m6 4 m 3/2
4n 'v =47! -——n 22 —— (—5—)
J (3J5c3m3 gt. ) [J17 RT,

1 2H, °° 4,929" "1,111

— — - v . , d — .
(2) ( m, )1; e 3‘" '0 2k]; (6 .1 5)
By defining 35(1), T,) as the velocity-averaged Gaunt factor. eq. 6. 15 can be integrated
to give

3219/2652? 2m, -h ulH’,

41'“IJ =
3312m§c3 tr, 850). Telni'nec
=6.84 x 10"”21nineTe‘Vzgflw. T,)e"‘”/”'erg cm‘Z’s‘l Hz“.
(6.16)

Due to the exponential term. f—f emission is more important at radio frequencies
than at optical frequencies. At radio frequencies, exp(—hv/kT,) ~ I. and the Gaunt
factor can be approximated by

_ J5
gfl-(u, 1",) — 7r [I7.7+ ln ( (v/HZ)Z
(Ia/103” . (6.17)
1‘78 Continuum Radiation in the Gas Phase

Thennalf—f emission is also an important source of continuum radiation in the

X-ray. An approximate form of the Gaunt factor in X-ray wavelengths is

J? h
330’. 7“,) = —H— In (It—1%) . (5.13)

Since the number densities of heavy elements are much lower than those of H
and He. they only make minor contributions to the total f—f emission. [f the He to H
number ratio is y and the fraction of He in singly ionized form is y’. then the singly
ionized He to H ratio is y’y and the doubly ionized He to H ratio is (l — y’) y ifthere is
no neutral He. If the number density of ionized H is rip. the electron density ne = 1913‘”
where x, = 1 + yy’ + 2y(1 — y'). The mean atomic weight per electron is then
1+4)!
11': =— . 6.
1+.vy'+2y(l -:v') ( I9)
Taking into account the difference in Gaunt factors. we can modify the emission
coefficient from that of pure H by the factor

n(He+) 7 :1 (1-16”)
Y=l+———+3 (6.20)
”p ”t1
For y = 0.” and y'=0.5. 1,, tie, and l’ have values of l.l?. 1.24. and [.26. respec-
tively. The total emissivity at low frequency is therefore

41:10 = 6.34 x 10"35nenpgfiw, 1;, z = 1)r;1/2r erg cm—3 5" Hz". (6.21)
Note that the emission coefficient has no frequency dependence ether than in the
Gaunt factor. Free—free radiation from an optically thin ionized gas cloud will tl'ten-
fore havean approximately flat spectrum. The only frequency dependence comes from
the Gaunt factor. which has a form of 1"“ in the radio wavelengths. From eq. 5.115.
the optically thin flux at distance D is

41!} 43.236)
F = ” —— . 6.22
V 41:02 ( 3 ( J
For R=O.l pc, 0: 1 kpc,£=0.6. up: 103cm-3, and 15:10“ K.the total
flux received at 5 GHz is ~ 0.3 Jy.
In the expression above for the total flux, we have assumed that the source
function BATE) is a constant throughout the nebula. The value of 1‘IE is determined by
the balance of heating by photoionization and cooling by recombination. forbidden-
line. and f—f radiation (Section 6.5). Since the nebula is usually optically thick in
the Lyman continuum (Sectiou 4.1). photoionization is mostly due to difl‘use Lyman
continuum photons and not direct starlight. As a result, T, is not a strong function
of distance from the central star. Also the forbidden-line cooling rate increases With
 6.3 Free-Free Continuum Emission 179

increasing 1". which controls changes in 1“,. confining the kinetic temperature to a
limited range of values throughout the nebula.
The absorption coefficient can be related to the emission coefficient through
eq. 2.70:

j”
Iv -_ __ 6.23
B.” ( )

This is valid so long as the velocity distribution of the particles obeys the Maxwellian
distribution. Combining eqs. 6.23 and 6.2!. we have the following expression for the
f—f absorption coefficient:

x, = 3.69 x roar; r I 2 w 3 my. 1“,. z =1)(1— e - In)”;

"” car 1 . (6.24)
For hu/kT, << 1.
xv = nomgfiw. T,)v'2T:3nn,nP r cm“. (6.25)
Foranebula with R =O.l pomp = l03cm'3. n, = l.l7np, l" = 1.26, and T, =104
K. gfl- = 5.1 at v = 5 GHz and the optical depth through the center of the nebula is
1., = Ethicu (6.26)
= 3.3 x :04. (6.27)
Because of the v"2 dependence. an ionized gas cloud is more optically thick at
lower frequencies. At sufficiently low frequencies, the cloud will become optically
thick and resemble a blackbody at temperature T,. The emergent flux is therefore
given by

r“) = 921w 3,17,) (6.28)

._ 2 2H"e 2
—Jr9 c2 v [or
hv
__ (<1.
ltT, (6.29)

where 6 = R/ D is the angular radius of the cloud. The spectral index. defined as the
slot», of the radio spectrum (gfigl), therefore changes from 2 at low frequency to
—0.l at high frequency (Fig. 6.4).
Since the recombination lines and the f-f continuum radiation come from the
same ionized region. the f—f flux is related to the flux of recombination lines such as
Hfi. Taking the ratio of eq. 5.! l5 and eq. 6.22 and using the H6 cfl'eetive recombina-
tion coefficient for T, = 10‘ K. we have
FH,(erg cm‘2 s") = 3.53 x 10""t"I FsGHzUy). (6.30)
In eq. 6.30 the flung for H6 and f—f are in different units. The monochromatic
fitur of a continuum radiation is measured in units of specific flux (Fv). whereas line
180 Continuum Radiation in the Gas Phase

‘t l—' I l l l l' I I fr‘l 17171 171 ‘l

l-

l
2.6

I
L.

I
2.4
l'

l4
2.2

LJJALLAI
2.0 L—
log F. (m
r

1.3 L-
L
1.6 l—

LLLJJ
i
1.2 r.-

LO

1—}
0.8 _l_ J— _|_ J— _l_ J— _._ _|_ I l l l I l n l l l l

.3 a
3.0 3.2 3.4 8.6 3.3 9.0 9.2 9.4 9.5 9.3
log v (Hz)

Figure 6.4
Thcf—f spectrum of a fully ionized. uniform-density sphere calculated using eqs. 2.82 and
6.24.

fluxes arein units of integrated flux (erg cm 2 s "). Since the observed Hfi flux is often
affected by interstellar andlor circumstellar extinction (Section ID. I). the comparison
between the expected Hfl flux given by eq. 6.30 and the actual observed flux will give
an estimate of the amount of extinction.

6.3.1 Total Energy loss

The total energy loss rate due to the f—f process over all frequencies is given by

Afi=ff 4njvdvdV
0
, 0) 'III
:63 x 10'3‘YT;'-'2(n,n,eV)f gfle‘mduergs"
o
= 1.43 x lO'ZTTe'izgfiYntnpeV erg s". (6.31)

where En is the average Gaunt factor and has a value of ~ 1.3. In a nebula of radi‘fS
0.1 pc. filling factor 0.6. and H density 103 cm 3. the total energy loss due to .H' 15
2.0 x 103‘ ergs“'. or ~ 5L0.
 6.4 Electron Scattering 101

6.3.2 Derivation of Cloud Mass from the Free—Free Flux

The ionized mass (M;) of a spherically symmetric, uniform-density. fully ionized gas
cloud is given by

4n
M,- ; Emigmflenf. (6.32)

The electron density can be expressed in terms of the S-GHz flux through
eqs. 6.21 and 6.22. Assuming y = 0.] l, y’ = 0.5. and T, = [04 K, we have

anc = 2.3 x lO'ng'gHze‘ '-’2R,'3-""D cm 3

= 1.5x 105[FSGHZ(Jy)]""2s 1--"2(ta,ran:sec)’3-"2(t),tkpc) mom 3,
(6.33)
where 9 = Ri/D is the angular radius. SubSIituting eq. 6.33 into eq. 6.32, we have

M,- = 2.45 x 10‘"Fs'gmeliztfl‘letasv‘2 g

= 2 x to ’3 [F5(;"z(1y)]l"'2 e '-"2(tat,ra:csec)3f’(oncpc)”2 Me. (6.34)
The mass of an optically thin ionized gas cloud can therefore be obtained by
measurements of its f~f flux and angular size assuming the distance is known.

6.4 Electron Scattering

Another source of continuum nebula emission is electron scattering. For example,

electron scattering is a major contributor to the continuum visible light of novae. If
the nova envelope is Optically thick due to electron scattering. then the optically thick
surface will act as a pseudo photosphere.
The cross section for electron scattering is independent of frequency and is given
by eq. 5.52:

2 2
a,-8—”( ‘3 ) _ (6.35)
3 trier:2

The mean free path of a photon in an ionized cloud of electron density n, is

1
l:
"90!

_ 1.5 x l0“ cm
(6.36)
(totem 3)
132 Continuum Radiation in the Gas Phase

and the corresponding optical depth due to electron scattering is

r=fn¢oeds

.—. 2 x [0 6(n,/cm'3)(L/pc). (6.37)

In stellar interiors. where almost all atoms are completely ionized by collisional
ionization. electron scattering is the dominant contributor to the optical depth. In
stellar aunospheres where more and more ions recombine with electrons. bound-flu
absorption becomes increasingly important. As we can see from eq. 6.36. the M
free path of a photon between electron scatterings can be very short under the high
density environment of stellar interiors.

6.5 Heating and Cooling of Photoionized Regions

Since stars are the primary source of energy in the ISM (others being cosmic rays and
cosmic background radiation). gas and dust acquire finite temperatures as a result of
either radiative or mechanical interactions with stars. The steady-state temperatures
of the interstellar gas and dust components represent the balance between heating
and cooling mechanisms. In H I] regions, planetary nebulae and active galactic nuclei
where there is a hot central energy source, the gas is mainly heated by pholoionization
(b—f). The energy of the Lyman continuum photons is convened to kinetic energy of
the free elecuons after overcoming the energy of the potential well. In general, the
hotter and more luminous the central source. the more Lyman continuum photons it
will emit, resulting in higher kinetic temperatures for the free electrons. Additional
heating can also come from the photoelectric effect on small grains mixed with the
ionized gas (Section 10.9).
In an ionized nebula. thermal energy will be lost when a free electron recombines
with a proton and transfers the kinetic energy back into potential energy of the bound
electron. In the following cascade. the potential energy is converted to line radiation.
If the line is optically thin. this energy will escape from the system (cloud or galaxy).
The gas can also lose energy by collisional excitation of atoms. The kinetic energy
lost during inelastic collisions between electrons and atoms will be converted to line
radiation. if the collisional de-excitation rate is low in comparison to the spontaneous
decay rate.
Assuming that an electron captured in H recombination will quickly cascade to
the ground state and all photoionization Occurs from the ground state. the heating rate
due to photoionization is given by

rm. 1,) = mnpaamnietrg. (6.33)

where E, is the averaged ltinetic energy of the ejected electron. As before, we 335"”
that the phoroionizatiOn rate over the entire nebula can be approximated by the total
recombination rate to all the excited states. In this case. every stellar Lyman continuum
 6.5 Hearing and Cooling ofPhoroionized Region: 183

photon will inject h v — h 1:. amount of energy into the kinetic energy pool and the rate
of total kinetic energy input is

E',(r,)=4nR§ f Way. (6.39)

”I hv

In cases when: the central source is not a blackbody. the Planck function in eq. 6.39
should be replaced by the appropriate flux distribution. in the photoionized regions
in active galactic nuclei, the central sourCe would be the accretion disk. Even for
stars. the blackbodies are often poor approximations and stellar atmosphere models
of the appropriate temperature and gravity would give better estimates to the Lyman
continuum output and therefore the heating rate.
Dividing eq. 6.39 by the total number of Lyman continuum photons (eq. 4.49).
we have

s, = £5. (6.40)
(2
However. this injection into the kinetic energy pool is reduced by the energy loss
due to recombination, so the net heating rate as a result of photoionization and
recombination is
m nkl a;
rung, Tc) =n,n,, (aBE, - Z E f émeuzangvfw, may). (6.41)
n=2t-0 0
Due tothe low spontaneous decay rates (and therefore the absorption coefficients)
of forbidden litres. all forbidden lines can be considered to be optically thin. Line radi-
ation from collisionally excited lines therefore represents a major cooling mechanism
for ionized nebulae. For each line. the cooling rate can be written as

AFLU-e) = "eEij("jer(T¢) — flrC:j(T¢))- (6-42)

The second term on the right is to account for energy gain due to collisional de-
excitation. The relative population it, and nJ- can be determined from the statistical
equilibrium equation as discussed in Section 5.]2.
Radiative cooling in an emission nebula serves as a thermostat to maintain
the electron temperature at a fixed level. If the kinetic temperature of the electron
increases, this higher temperature will lead to a higher collisional excitation rate.
which will lead to a cooler nebula as a result of increased rate of emission by
collisionally excited lines. Figure 6.5 shows the comparison between the heating rate
by photoionization for a 35.000~K star and the cooling rates by different radiative
processes. The equilibrium electron temperature is about 8000 K.
Although the central star is often the sole source of energy in an emission nebula.
the electron temperature in the nebula is not sensitive to the distance to the central star.
This is because the majority of the electrons are ejected by diffuse Lyman continuum
photons, and not by direct starlight.
[B4 Continuum Radiation in the Gas Phase

—23 r l I T t I

llrll
log [Heating or cooling rate/n'np (erg cmJ s '-)]

Free—
4000 6000 3000 10,000
Temperature (K)

Flgure 6.5
The balance between heating and cooling rates in an ionized nebula with a central star of
35.000 K. The solid lines show the cooling rates due to various collisionally excited lines
(eq. 6.42). The cooling rate by f—f continuum radiation (eq. 6.3l) is given by the dotted
line. The sum of all cooling rates is given by the solid line labelled "Cooling function
A(T).“ The equilibrium temperature is given by the intersection of this line with the heat
rate by photoionizalion (dashed line) (eq. 6.4!) (from Spitzer 1978. Physical Processes in the
Intensrettar Medium, Wiley, New York. p. 137).

Since collisionally excited lines of metals play a dominant role in the cooling
of an ionized nebula. a metalifree H II region ionized by a primordial (Population
Ill) star will have much higher electron temperatures than galactic H 1| regions. Such
higher electron temperatures lead to a more significant role for electron collisions in
the excitation of the H atom. The net effect is that the populations of all levels of H
are increased and all recumbination lines are strengthened. Because of the e‘E’”
factor, the lower levels are favored, and the strengths of the Lyman a and Her lines
can increase significantly over the Case E values. This in tum leads to an increased
amount of two-photon radiation. as the population of the 2: state is increased as a
result of collisional excitation from both It and 2p.
In diffuse interstellar clouds where there are no hot central stars to serve as the
heating source, the major heating mechanisms are photoionization of heavy elemenls
(e.g.. C. Mg, and Si, whose ionization potentials are lower than that of H; see Table
A2. I) by diluted starlight. and collisional ionization of H by cosmic rays. The heating
equation will no longer been dominated by the photoionization of H and will consiSl
 6.6 Determination of the Temperature ofrhe Centmi Star by Nebuiar Properties IBS

of several terms. each similar to eq. 6.38. instead of a central source of flux tr B(T_) in
eq. 6.39, the photoionization source is external and is given by the diffuse interstellar
radiation field (Section 4.7).

.55 Determination of the Temperature of the Central Star by Nebular Properties

The central stats of H n regions and planetary nebulae are difficult to study because
of their faintness in the visible (due to their high temperatures) and the contamination
of their spectra by nebular emissions. However. since the central star is the ultimate
energy source of the nebula, then nebular emissions (atomic lines. dust continuum.
etc.) can be used to infer the luminosity and temperature of the central star. For
example, since the H absorption coefficient for Lyman continuum photons is high,
recombination lines can be used to infer the stellar temperature. Dense dust clouds
can be completely optically thick in the visible. and the dust continuum radiation
can be used to infer the total flux (and therefore temperature) emitted by the central
star (Section 10.3.2). Below. we describe two methods with which the central star
temperature can be determined from the nebular spectrum.

6.6.1 Zanstra Temperature

The method for deriving the central star temperature by comparing the nebular
recombination flux with the stellar continuum magnitude was developed by Zanstra in
1927. This method is based on the assumption that the number of Lyman continuum
photons absorbed in the nebula is equal to the total number of recombinations to all
levels excluding the ground state. Since the nebular H13 flux can be related to the total
number of Lyman continuum photons. T. can be derived by comparing the 1-1.6 flux
with the stellar V magnitude.
The ratio of the total nebular Hfi flux to the stellar continuum flux at V band is

FHfi _ hum, fngnptrfffldv

_ (6.43)
F..(V) 4n R217 BAT.)

Substituting eqs. 4.50. 4.55. and 4.56 into eq. 6.43. we have

r"5 15m of"

— ___._"’ a-"irfotr.t (6.44)
mvi - n5k3.(r.) :13
Since the ratio of craft, to an is independent of T‘. the central star temperature T, can
be determined from eq. 6.44 by iteration.
The fact that stellar atmospheres are not well approximated by blackbodies
may contribute to errors in the Zanstra temperatures. The main problem remains.
however. that this method requires the measurement ofthe stellar magnitude. Since the
nebular continuum is often brighter than the stellar photospheric continuum (Fig. 6.3).
measurements of the stellar V magnitude can have very large errors. or be simply
impossible.
[36 Continuum Radiation in the Gas Phase

6.6.2 The Energy-Balance Method

The energy-balance method was first introduced by R. W. Stoy in [933. It avoids the
assumption of optically thick H l (or He II) as required by the Zanstra method, and
instead um the nebular forbidden- and recombination-line ratios to determine the
central star temperature. If the mean energy of the electron'IS ngg. then threshold
energy available for the excitation of forbidden linests

3
Irv, = but + 51:11.. (6.45)

Since each photoionization can produce h(u — vs) amount of energy available for the
excitation of forbidden lines, the total amount of energy emitted in forbidden lines is
therefore
one
41:02:?” = 4n Rf f —"
Tr“) Mu — De} dv. (6.46)
v
”I

where FH. is the total flux observed in forbidden lines. The total power radiated in
the recombination line Hfl is

41rD2FHfl=thfi f Mpaflgdv. (6.47)

Dividing eq. 6.46 by eq. 6.47 and making use of eqs. 4.49 and 4.50, we have

fa- ., enema»
PH, «.39th ff“Nd '
(6.48)

By summing up the fluxes in all forbidden lines and comparing the sum with the
flux in H5. T, can be found by iteration using eq. 6.48. However, it is difficult to
include all the fluxes of collisionally excited lines. in particular those in the UV or in
the infrared, and collisionally excited H l lines. The stellar temperatures derived by
this method can be considered as lower limits.

6.7 Summary
While the blackbody radiation is the most familiar and conunon form of continuum
radiation, low—density ionized nebulae can radiate continuously [trough the f—b.
f—f, electron scattering. and 2-}! processes. These processes have unique frequency
dependencies and spectral shapes that allow us to separate them from other continuum
radiation such as diffuse starlight1 cosmic background radiation. and dust emission-
By measuring the continuum fluxes emitted by theSe gaseous materials. we can use
them as probes of the physical conditions of the ionized nebulae as well as their energy
sources.
 Exercises 187

Exercises
1. Find the b—f absorption coefficient for neutral hydrogen in a stellar atmosphere of
temperature 5000 K. Assume that the atmosphere is made of pure hydrogen with
no other elements and 3st = l for all states. Plot log K as a function of log It in the
wavelength range of 100 A-l um.
. A completely iouized spherical gas cloud made up of 100% H has a density of 100
atoms cm 3‘, a temperature of 10,000 K, and a radius of 0.2 pc.
(a) Assuming the Gaunt factor to be I at all wavelengths, calculate the emission
coefficients (j) forf—f, b-f, and two-photon (Case B) processes.
(b) Assuming that the density is uniformly distributed within the cloud, calculate the
maximum optical depth through the center of the cloud at 0.5 pm, 1 um. 10 um.
and 1cm.
(c) Calculate and plot the total flux emitted by the cloud between A01 ,um and 1 cm
as observed by an observer at a distance of 1 kpc. Justify any assumptions used.

. Calculate the net heating rate due to photoionization and recombination (F/npn,
in units of erg cm3 s") for a central star of temperature 35.000 K in a nebula with
T, = 4WD. 6000. 301]). and 10,000 K. Use the values of as calculated in Exercise 3
in Chapter 4 and assume all Gaunt factors to be 1 in the calculation of ant-
. Assume that the solar atmosphere consiSIS of mostly neutral H at a temperature of6000
K and a number density of 10'0 ant-3. and that b—f andf—f are the dOminant sources
of opacity. Calculate the physical depth at an optical depth of l at the wavelengths of
1000 A. l um. and 1cm.
,,Z
Interstellar Molecules

Interstellar molecules were first discovered in the late 19305 through the identification
of optical lines seen in absorption against background starlight with electronic transi—
tions of molecules. The molecules first detected were CN (322+ — X2 2"" at 3376.84
A; for the spectroscopic notation for the electronic states of molecules. see Section
7.2). CH (.4201 — xzn at 4300.30 A) and CH+ (A'll — x'z’r at 4232.54 A). When
radio receivers became available in the early 19505. spectroscopic observations of
molecules in the radio region became a real possibility. The AIS-cm transition of 0H
was predicted by losif Shklovslry and Charles Townes in 1953 and was detected 10
years later. in the late 19605, the molecules ammonia (NI-l3, at A13 cm). water (H20.
at 1.1.4 cm). and formaldehyde (HzCO. at 16.2 cm) were detected. With the develop-
ment of millimeter-wave receivers. the rotational transitions of many molecules were
detected in the 19705. Early detections included carbon monoxide (CO. at 12.6 mm)
and hydrogen cyanide (HCN, at 13.4 mm).
At about the same time, spectroscopic observations in the near infrared made
possible the observations of the vibrational transitions of molecules. Among the first
molecules detected in absorption against the infrared dust continuum of evolved stars
were CO (v = 1 —> 0 at 4.7 pm. Section 7.5). acetylene (Cszv C—H stretch at 3 pm),
and HCN (C—H stretch at 3 tun. Secuon 8.1). Also present in the near-infrared
spectrum of cool. evolved stars are the electronic transitions of carbon molecules.
for example, the lt'll,‘r — X'E; Phillips system of C2 and the A211 — X21.” Red
system of CN. For molecules without a dipole moment (e.g.. H1. H; CH3, C2H2.
and CH4). which therefore do not have electric-dipole rotational transitions, infrared
techniques remain the main means of observing them. As of 2005, over 120 interstellar
molecules have been detected using the techniques above (Table 7.1).
Strong absorptions by H20, 02, C02. and CH4 have made the Earth’s atmosphere
opaque over much of the mid- and far-infrared spectral regions. Since the IOvv-energy
bending modes of molecules (Chapter 3) lie primarily in the far infrared, they can be
detected only from telescopes placed on high-flying aircraft or satellites.
One of the most interesting aspects of interstellar chemistry is the possibility of
studying molecules that do not occur naturally on Earth. Many radicals too short—
lived to be observed in the terrestrial envinonment are abundantly present in the [SM
because of the low-density conditions. Examples of molecules identified in Space
prior to their being studied in the laboratory are the linear acetylenic chain radicals

189
190 lnten‘tellar Molecules

Table 7.1
Interstellar molecules liSlcd by number of atoms
fi—--..
Four Five 51: Seven Eight
Diatomic Tl'ifllornic atom atoms atoms atoms atoms

H; C; c-C3H C5 C5H Cal-l CH3C3N

AIF CZH l-C3H 04H l-H2C4 CH2CHCN HCOOCH,
MCI C20 C3N C4Si CIH. CH3C1H CHJCOOHC?)
q C28 C30 l-C3H2 CHJCN HC5N C7H
CH CH: CJS c-C3H2 CH}NC HCOCH, H2C5
CH+ HCN CZHI CHZCN CH30H NHICH3 CHZOHCHO
CN HCO CH,D+(?) cm CHJSH cczmo CH2CHCH0
C0 HCO+ HCCN HC}N HCJNl-I" CHZCHOH
CO’r HCS+ l-ICNl-l+ HCZNC HC2CH0
CP HOC+ l-lNCO HCOOH N'l-lzCHO
CSi H20 HNCS HZCHN C5N
HCI H25 HOC0+ HZCZO HC4N
KCI HNC HZCO HzNCN
NH HNO H2CN HNC;
NO MgCN HZCS SiH4
NS MgNC [130+ HZCOH“
NaCl N2H+ NH3
OH N10 SiC3
PN NHCN C4 Nine Ten EIeVen Twelve “Meet:
80 OCS atoms atoms atoms atoms atoms
50* SO: CHJC4H CHJCSNt?) HCgN CHJOCZH, HCHN
SiN c-SiCz CHJCHICN (CI-l3)2C0
SiO C02 (CH3);O NHICHZCOOH
Sis NH: CHJCHZOH CH3CH1CHO
CS H; HC1N
HF SiCN CEH
SH AINC
FeCH'?) SiNC

Table from A. Wooflen (www.cv.mo.uiul~awootterflallmols.hlml).

 Interstellar Molecules I91

CflH (n = 2. . . . 8) (Section 3.4) and cyclic molecules such as cyclopropenylidene

(C3H1. Section 7.9.4). Therefore. the need to identify interstellar lines serves as a
great motivator for laboratory studies of radicals.
The detection of molecular lines in emission suggests that the vibrational and
rotational states of molecules can be excited by radiative or collisional means in the
ISM. The measurements of the strengths of lines from different rotationallvibrational
states can therefore serve as effective probes of the temperature. density. and radiation
background of the ISM (Chapter 9).
Although the physical conditions of the ISM are generally not energetic enough
to excite the electronic states of molecules, interstellar molecules in the line ofsight of
hot stats allow the electronic transitions to be observed in absorption. The availability
of telescopes in space made possible the detection of ultraviolet electronic transitions
in absorptiou. Molecules detected in the UWoptical include H2, OH. NH, CH. CH+,
CN. C0, C1. and C3 (Section 7.6).
Molecules play an important role in the energetics of the ISM. Stars are formed
as a result of the gravitational collapse (Section l5.4) of interstellar clouds. and such
collapse is possible only if some of the gravitational potential energy of the cloud can
be radiated away. Molecules such as H20 and C0 are particularly effective coolants
because they have low-lying states with E/k 5 30 K, which can be easily excited by
collisions. The kinetic energy of the colliding gas (primarily H2) is first transformed
as internal energy of the molecules and then lest as line radiation as the molecules
undergo spontaneous decay to the ground state.
The detection of molecules in planetary atmospheres. comets. stellar atmo-
spheres. circumstellar envelopes. and interstellar clouds suggests that molecules ofex-
traterrestrial origin are common. Since all heavy elements are made in stars. molecules
(with the possible exceptions of H2. HD, HeH+. LiH, etc; see Section l7.3) cannot
be primordial and must be synthesized from atomic species via chemical reactions
(Chapter 14). If the abundances of different molecules can be determined accurately,
then the variation in abundances in different environments can tell us how chemical
processes work under different physical conditions. For example, molecular clouds
in the surroundings of hot stars with strong qu-aviolet background radiation can serve
as a laboratory for photochemistry.
Comets are believed to be bodies left over from the primordial solar nebula. and
their chemical compositions may represent the state of the ISM from which the solar
system was formed (Section 13.5. I). As comets approach the Sun, sublimation from
the cometary surface causes gaseous molecules to be released. Molecular species
detected in comets include H20, CO. HCO+. HZCO. CH30H. HCN. HNC. CH3CN.
CS. OCS. H25, HCJN, HNCO, HCOOH. CH3CHO. C02, CH... C: H2. and Czflg.
This large variety of molecular species in comets therefore gives us a glimpse of the
chemical richness of the primordial solar nebula and a connection to the molecular
cloud from which the solar nebula was formed.
Through the determination of relative abundance of interstellar molecules, we
believe that molecules are constantly being made and destroyed in the ISM through
gas-phase or grain-surface chemistry (Chapter 14). More definitely. we know that
191 Interstellar Molecules

molecules are being synthesized in the circumstellar envelopes of asymptotic giant

branch (AGB) stars. and a variety of molecules are being ejected into the ISM by AGB
stars in the form of stellar winds (Section 15.7). Molecules detected in the carbon stai-
CW Leo (lRC+l0216) include carbon chain radicals (up to Call). cyanopolyyncs
(up to HCgN), and sulfuretted chains (up to CCCS). Because of the short dynam-
ical scales (~104 yr) of the circumstellar envelopes where these molecules are
found, there is no doubt that molecular synthesis is very efficient in the circumstella:
environment.

7.1 Molecular Transitions

Vibrational and rotational states of molecules can be excited either collisionale or

radiatively. and the observations of these transitions allow new ways to probe the
physical structure of ISM. Because the vibrational and rotational states of molecules
have much smaller energy separations than those of electronic states, the Vibrational
and rotational transitions occur, respectively. in the infrared and millimeter-way:
regions of the electromagnetic spectrum instead of the visible and near UV as in
the case of electronic transitions. This in turn requires that new techniques be used in
the observations.
Due to the very different energies of the electronic, vibrational, and rotational
states. these interactions can be assumed to be decoupled and their respective wave-
functions separable. The separation of nuclear and electronic wavelunctions is re-
ferred to as the Born—Oppenheimer approximation and its adoption greatly simplifies
the handling of the quantum mechanics. Under the Born—Oppenheimer approxima-
tion, the total wavefunction is a product of the nuclear. electronic. vibrational. and
rotational wavefunctions:

‘l’tot = 'l’nucwel Wroclaw (7-!)

Although this forms the basis of our following discussion. it should be remem-
bered that effects ignored in making the Born—Oppenheimer approximation can yield
interesting astrophysical results. The most well-known example is the interaction be-
tween the rotation of the nuclei and the electron orbital angular momentum, which
leads to a splitting of the non-E electronic states of diatomic and linear molecules
known as A doubling (Section 7.10.1).

7.2 Electronic Structures of Molecules

The notation for the electronic structure of molecules is similar to that for atomic
structure under L—S coupling (Section 4.2). Each electronic state is designated by
”HA9. where S is the total electronic spin and A is the projection of the total
electronic orbital angular momenta along the internuclear axis. The uppercase Greek
letters E. H. A, . . .arcused to represent A = 0. I. 2, . . . ,analogoustothe notation
 7.2 Electronic Structures of Molecules [93

used in atomic structure. 9. the projection of the total electronic angular momentum
onto tlte internuclear axis, is given by the sum of A and E. where 2 (not to be
confused with the state designation for A = O) is the projection of the electronic spin
angular momenta along the internuclear axis. The value of E ranga from —.S' to +3
in increments of t. For example. a 21'] state has 2H3]; and 211.]; (corresponding to
|A| = l, E = :l: 1/2). Unlike atomic notation, the values of Q, A. and E can be added
algebraically rather than vectorially because they all refer to the same projection.
1f the electron wavefunction of a E state changes sign when reflected about any
plane passing through both nuclei, it is denoted as E‘; if unchanged. then 2*. For a
molecule with two identical nuclei (e.g., H2, Q). the right subscript 3 (even) refers
to the fact that the electronic part of the molecular wavefunction of this state remains
unchanged on reflection through the center of the molecule. and it (odd) refers to a
sign change.
The elecn'onic states of diatomic molecules are also labelled with letters: X is
used for the ground state, while A, B. C. . . . are used for excited states of the same
multiplicity (ZS + 1) as the ground state. States with a multiplicity different from that
of the ground state are labelled with lowercase letters (a. b. c. etc.). For example. the
ground state of C2 is X 12" and the lowest excited state is can". Since the ground
state has a multiplicity of l and the first excited state has a multiplicity of 3. the excited
state is labelled a.
The electric-dipole selection mles for electronic transitions in a diatomic mole-
cule are

AA=0,:l:l.e.g., E — )3,“ — E.A—l1,etc.

0 AS=O
' A9=0.:l:l
- E+—E+.E"— 2",butnot E+—E"
. 34.,“

In the interstellar medium. the H2 molecule is generally in the ground electronic

state X '23”. As a result of the AS = 0 selection mle, the transition from the ground
state to the first unbound state b3 E; is not allowed (Fig. 7.1). thereby protecting the
molecule from photodissociation (Section 14.2).
An electronic transition consists of vibrational bands. which in tum are made
up of rotational uansitions (Section [4.2). Common molecular electronic transitions
observed in the photospheric spectra of cool stars include the Swan band of C: (Table
7.2) in carbon stars and ”110 in oxygen-rich stars.
The electronic structure of polyatomic molecules are much more complicated
than diatomic molecules. The spectroscopic notation is related to the symmetry group
of the molecule. For example, H20 belongs to the point symmetry group C2,, and its
gg'gmnd electronic state is written as J? 'A.. For CH2. the ground electronic state is
x 3,.
194 Interstellar Molecule:

— 20

l50.003- H(n=l)+p

UH-H

15

l00,000 - (ev)

‘m' - l0

50.000—
H(nal)+H(n=l) - 5

o-__- : ........................... o
l l l l
0 l 2 3 4
R(lO"cm)

Figure'lJ
Energy diagram of the lower electronic states of H1. The short horizontal lines in each of
the bound states indicate the vibrational levels. The transitions from the ground state ‘2:
lo the excited states '2: and '11,, are called Lyman and Werner bands. respectively. (Fist-ll:
adapted from Watson. 1975. in Atomic and Molecular Physics and the Interstellar Matter. L15
Houches, p. 177.)
 7.3 Molecular Orbital: and Hybridization 195

mils 72
Electronic transitions of C2

Band Transition Spectral region (um)

Ballilt—Rarnsay bJE; — 43”, 2.700—IJOO

Phillips A'n. - X's; 1.5494612
Swan ding—En, ones—0.340
Declaridres-d'Aumbuja c'n, — x'rl. 0.4] l-0.339
Fox-Henbet'g einl — a3n. 03294.23?
Mullilten 0'2: — xix; 0242—0231
Freymark 51:; - A'n. 0222-0207

Adaptai from Table 6. ID in IN. Hollas, High Rtsoltulon Spectroscopy

7.3 Molecular Orbitals and Hybridization

While the structure of atoms can be specified by their electron configurations consist-
ing of atomic orbitals. elections in a molecule can be considered to be shared by more
than one atom in a molecule. Such sharing of electrons leads to molecular orbitals.
The simplest example is the hydrogen molecule (H2), where two 15 electrons with
antiparallel spins overlap to form a covalent bond known as the a bond. 1n the case of
carbon. which has four valence electrons (2s and 2p). a variety of possibilities exist.
Take the case of methane (CH4) as an example. The four C—H bonds in methane are
all identical and form a tetrahedral structure. with each H—C—H forming an angle
of l09.5°. This mixing of atomic orbitals is known as hybridization and is labelled as
sp3. which is the most common hybridization for carbon.
If the 2: orbital combines with only two of the three available 2p orbitals. the
result is a planar structure with a H—C—H angle of 120°. This is known as spz
hybridization. When two 5;)2 hybridized carbons approach one another, they form a
a bond by sp2 -— sp2 overlap, whereas the unhybridized p orbitals on each carbon
form 1'! bonds on the side. The combination of the er and Jr bonds results in the sharing
of [our electrons and the formation of a C=C double bond. An example is ethylene
(H1C=CH2). which is a planar (flat) molecule with the two carbon atoms connected
by a double bond.
One of the most interesting examples of the sp2 hybridization is the benzene
(Cal-l5) molecule. The six C atoms of benzene form a symmetric ring structure. each
with a H atom attached. Although the structure of benzene is often schematically
represented by a hexagonal ring with six C atoms at the corners and alternate single
and double bonds between them. in fact all six carbon-carbon bonds are equivalent.
Molecules with such tinglike structures are referred to as aromatic compounds.
196 Interstellar Molecules

When two or more rings are fused together. they are called polycyclic ammu‘.
molecules.
A third form ofhybridization for carbon occurs when the 2s orbital combines With
a single 2p orbital. which forms a linear structure with the remaining two 2p orbitals
unchanged. This is called sp hybridization, and acetylene (C2H2) is an example of
such a structure. The two sp-hybridized carbon atoms are joined by one sp—sp a bond
and two p—p rr bonds. resulting in a linear molecule with a H—C—C bond angle of
130°. The carbon atoms are joined by a triple bond. and the structure of acetylene can
be written as H—CEC—H.
Because of the availability of these hybridizations. the carbon atom is extremely
versatile and can form a wide variety of molecules with hydrogen. oxygen, nitrogen.
and so forth. For comparison. the only stable molecules that oxygen can form With
H are water and hydrogen perortide (H202). For nitrogen. the only stable molecules
are ammonia (NI-l3) and hydrazine (N2H4). Since H and C are, respectively, 111: fig.
and founh most abundant elements in the universe. it is not unexpected that organic
molecules are present in the ISM.

7.4 Rotational Transitions

The rotation of a molecule can be described in terms of motions about the principal
axes. In general, a molecule has three principal moments of inertia id. in. (C. in
increasing order. If all three moments of inertia are different. the molecule is referred
to as an asymmetric top. If two of these moments of inertia are equal. the molecule is
refined to as a symmetric top. A symmetric top can be either prolate (like a cigar) or
oblate (like a pancake). Let us begin the study of the rotational spectra of molecules
with the simplest example. the diatomic molecule. which has 1,. = 0. [3 = 1c. The
roration of a diatomic molecule (such as CO} can be approximated by a rigid rotator
of moment of inertia

r = ml, (7.2)

where it is the reduced mass

_ ___’"1’"2 (7.3)
m. + m2 ’

m1, m: are the masses of the two nuclei. and r0 is the internuclear separation. The
energy levels of the rotational states are given by the solution to the Schrodinger
equation of a rigid rotator:

’12
E=——-JJ+]. (7-4)
I Bn2l( J
 7.4 Rotational Transitions 197

where J is the rotational quantum number. [n spectroscopy. eq. 7.4 is often written in
terms of the rotational constant B.

E; = 11810 +1). (7.5)

when:

it
3g — 7.6
3:72] ( )

has units of frequency. For electric-dipole transitions. only transitions between the
successive rotational states are allowed (73.! = :H). Therefore. the frequencies for
the transition from upper statet' to lower state j are given by

u..- = 230}. + t). (7.7)

Real molecules deviate from the rigid rotator approximation, and their rotational
energy states are approximated by fitting functions using coefficients D, H, . . . and
so on:

5, =71 [310 + 1) — DJZU +1)2 + HJ3(J +1)3 — - - ]. (7.3)

For the C0 molecule. 3, D, and H have values of 516359633 GHz. 0.1335055 MHz.
and 1.725 x 10‘7MH2. respectively. The lowest rotational transition, J = l -+ O, has
a frequency of 1 15.2712 611:. The higher rotational transitions of CO lie at terahertz
frequencies (Table 7.3) and have been detected by ISO (Fig. 7.2).
From eqs. 7.2. 7.6. and 7.7 we can see that the heavier the molecule, the lower are
the rotational transition frequencies. While CO (molecular weight 28) has a ground—
state rotational transition at 1 15 GHz. the corresponding transition for a light moleCule
can be in the terahertz (Tl-12) range. For example. CH+ (with a molecular weight of
13). has a rotational constant of 417.62 GHz. or a J = 1 —> 0 transition frequency of
835.2 GHz. Although this line is difficult to study using ground-based telescopes, the
higher rotational transitions of CH+ (from J = 2 -—> I to J = 6 —> S) were detected by
750. A number of common molecules have no elecuic-dipole moment (e.g.. H2. 01.
and N2) and therefore have no allowed electric-dipole rotatiOnal transitions. although
02 has magnetic-dipole transitions that are strong enough to block transmission
through the Earth‘s atmosphere. for example. near 715 GHz (see Figs. 7.3 and 7.14).
Figure 7.3 shows the submillimeter specuum of the Orion molecular cloud.
The spectrum is dominated by rotational lines of C0. C5. SO. SiO. HCN. HCO+.
HZCO. 302, and CH301-I. There are over 1000 spectral features in this spectrum.
corresponding to over 2000 lines (some partially blended). Approximately 14% of the
lines are unidentified. Because of the large number of molecular rotational lines in the
mm and submm regions. crowding has become a problem as the telescope sensitivity
improves. As more and more complex molecules are found. each of which has many
I98 Imersreflar Molecules

Table 7.3
CO rotational lines in the far infrared

1.- - J; 1 (pm) E1, tern")t

38-37 69.0744058 2690.99
37-36 709072390 2549.96

36—35 718428544 2412.68

35-34 74.8900599 2279. l 5
34—33 77.0586994 2149.38
33-32 79.3598104 2023.37
32-31 813058100 1901.13
31-30 84.4107173 1782.66
30-29 87.1904213 1667.97
29-28 90.1630019 1551M
28-27 913491227 1449.94
27—26 96.7725080 1 346.60
26-25 1014605323 1247.06
25—24 1044449505 1151.32
24-23 1083628094 1059.37
23-22 1114575993 971.23

22—21 1 18.5807176 886.90

21-20 1241933521 806.38

20—19 1303689279 729.68

19-18 1311963285 656.79
18917 1447841891 587.72
17—16 1512667064 522.48
16-15 1628116263 461.05

15—14 1716314272 403.46

14—13 1853992957 349.70

1 Wmnurnlxrs in uniu of cm" an oomonly used

as a measure of frequmcy in molten“: splecmoopy.
To obtain Ihe energy or the 01113100". multiply
m by ht.
 7.4 Rotational Msitr'ans 199

f
9
N

5
g T22-2I _T21—2o T2049 TIME Tia—11
L 1 I; L J l I l _I_ l _I_ l— l _I_ l— I _I_ l l

120 130 140 [so 160

32—3131—30130—29129—23 25—27'12-’35“126—25 125—24 12-1—23 :22 l q

r it.
3 .
1‘ ”I .1
“MATH“ ..;Q 132—31, 126—25 I Jg—za T_
4 r . r l . r r r I 1 r r r 1
5'0 90 [00 no 120
M}: m)

Figure 7.2
ISO long Wavelength Spectmmeter(LWS} spectrum ofAFGL 618 after subtraclion of dust continuum.
The rotational transilions of C0. li‘co. HCN, 3,0. and 0H are marked by arrows (from Herpin and
Ccrnicham 2000. ApJ. 530. L129).

weak rotational lines, these lines will form a continuum making the identification of
individual lines difficult.
Although the C0 J’ = 6 — 5 is the strongest line in lhe Orion spectrum. when all
the transitions of a molecule are considered, 50; and CH3OH have higher total line
strengths in the spectrum than CD. This suggests that these molecules are stronger
coolants than C0 in a star formation region.
200 Interstellar Molecules

]m l l— I I l I I 'I I I | ~1__‘

50 — _

l u

i 'I I III I I
0 l :
a: :

_ . 53 4
_ =3 =0 as 33 a
b
+' sO
Um s"-
s O C n :o L
O ‘
_

505! lessee s _51818i31 is,

650.000 700.000
Rest frequency (MHz)

Flgure‘l.3
The spectrum of Orion KL from 60‘}r lo 725 GHz taken at the Caltech Submillimerer Telescope.
Overlaid is a plot of the zenith atmospheric transmission for Al mm of precipitable water vapor
at Mauna Kea (altitude 4200 In). This region covers the 450-um window. bracketed by broad
atmospheric absorption by water at 557 and 752 GHz. The gaps in this spectrum at 620.7 and 7I5.4
GHz are due to atmospheric H10 and 02. respectively. The ordinate is the antenna temperature (in
K) for the spectrum and in % for the aunospheric transmission. The molecules responsible for some
of the strongest lines are marked by dotted lines below (from Schilke er al. 2000, ApJS. 132, 21%|).

7.5 Vibrational Transitions of Diatomic Molecules

Diat0mic molecules can also undergo vibrational motion (stretching of the molecular
bond) and the energy levels resulting from these motions are also quantized. lfwc
approximate such vibrations by a simple harmonic oscillator. then the solution of the
Schrodinger equation gives the following energy levels:

Eu = (v + éflwo. (7.9)
 7.5 Vibrational Transition: ofDiaramic Molecules 201

where v is the vibrational quantum number and

90 = ‘- - (7.10)

is the natural oscillator frequency and k is the spring constant.

From eq. 7.10 we can see that the vibrational frequency decreases with increasing
atomic mass. For example. v9 for a 0—H bond is approximately 2.5 times larger than
no for the C——C bond. Since the spring constant is higher for a stronger bond, the
vibrational frequency is correspondingly higher (e.g.I in a triple bond vs. a single
bond).
If a diatomic molecule is rotating and vibrating at the same time. the moment of
inertia changes with time due to the changing bond length. If the rotator is not rigid
(as it needs to be if vibrating). the atoms also experience a repulsive centrifugal force.
Consequently. the rotation constant is expected to be dependent on both 0 and J .
For a rotating harmonic osciallator. the energy levels are given by

£v_,=(u+%)hv+J(J+l)hB—
[BJ(J + 1)}2
(7-11)
(Inner; + 3310 +1)‘

where

1:1 6311 l
u: _r°_+___2(+)_ (7J2)
“’0

For most molecules, (Inflows is much larger than 33] (J + l) for small values of J.
and u can be approximated by a series expansion:

l l 2
V = —
”o[l+(2)l’ — —
(4)? + . . .
i. ( 7. 13)

where

=33](J+l)_ (7.14)
(unkrg
Similarly, eq. 7.] I can be expanded into

Ea: = (v +31% + hB’JU + 1) — hD'[J(J + 1)]1 + hH’UU +013. (7.15)

202 Intersteflar Molecules

where

‘1?
hvo

, _ 4335
— ——h4v4- (7.16)
Comparing with eq. 7.9, we can see that the first term of eq. 7.15 corresponds to the
energy level of a nonrotating harmonic oscillator. The following terms arise due to the
nonrigid nature of the diatomic bond. The second term originates from the vibration.
rotation coupling, and the third and founh terms are due to centrifugal distortiOn
(eq. 7.3).
The selection rule for vibrational transitions within the harmonic approximation
is Au = :hl. The ground-state vibrational transition (tr = l 4-) O) is called the fun-
damnrai transition, whereas transitions from higher excited states directly to the
ground state (u = n 4+ 0. n = 2. 3, 4, . . .) are referred to as overtones, and Mimi.
tions between excited states v = n’ 4+ n”. n” 5e 0, n' > n” are called hot bands. For
example. the fundamental (v = l <-> 0) and the first overtone (u = 0 4+ 2) transitions
of C0 are at 4.67 and 2.35 urn, respectively. These bands are commonly observed in
absorption against a background stellar or dust continuum (Fig. 7.4).

1.05

l_.I_r_l..|_l__r_l_A
Relative flux

PU]
M0]
0.35 t—
Rt!) “1)
0.30
R12]
M3)
0-75,' MonR‘ZIRS3

l l A I r L i .

2.3 l5 2.325 2.335 2.345 2-355

Wavelength (p m)

Figure 7.4
The CO v = 2 <— 0 vibrational overtone bands of C0 observed in Mon R2 with the Subaru
Telescope with a spectral resolution of 1/ AA. ~ 23.000 (data courtesy of M. Gate).
 7.5 Wbrarional Transitions ofDr'aJ'amic Molecules 203

The rotational transitions within each vibrational transition are organized into
branches according to the change in the rotational quantum number (initial minus
final in an emission process) AJ . The selection rule for one-photon, electric-dipole
transitions is AJ = —l and +1 (called .P and R branches. respectively). The frequen-
cies of the transitions in the fundamental mode are
u=vo+2(J+l)B 1:0, 1,2,... fortheRbranch
u=uo-—ZJB J=l. 2. 3,...forthePbranch. (7.17)

where bug is the energy between the ground rotational states of the vibrational
levels. These vibrational—rotational transitions are labelled as PU = l. 2. 3. . .) and
3(1 = 0, l, 2. . . .). where J is the rotational quantum number of the lower vibrational
state (Fig. 7.5).
The total angular momentum J of a linear molecule is given by the vector sum
1 = N + L + S +1, where N. L. S. and l are the rotational. electronic orbital. electron
.___ -.__......____..___._____-.._._-_____.

P(4) P0) PG) PH) V0 3(0) EU) R(2) M3)

.l

Frequency —I-

Figure 7.5
A Schematic diagram illustrating the P and R branches of the vibrational—rotational transitions
of a diatomic molecule.
204 Interstellar Molecules

spin. and vibrational angular momenta, respectively. Vibrational angular momentum

is present only in polyatomic molecules, and is often not discussed in elemnury
books on quantum mechanics. An example of the vibrational angular momentumis the
bending modes of linear polyatomic molecules (e.g.. HCN. Section 8.1). Since moat
common molecules have no electronic Orbital angular momentum and no unpaired
electron spin. I can be considered to be equal to N + I for most asu-ophyfiw
molecules. In that case, the possible quantum numbers for J are ll ,, H | + 1‘ . __
and so on. The two common exceptions are 02 (X 328) and NO (x 2n), 02 In;
unpaired electrons (S = l) and NO has nonzero electronic Orbital angular momentum
(A = l) and nonzero spin (S = 1#2).

7.6 Electronic "Ii-ansitions

Vibrational—rotational transitions between different electronic states can be observed

in absorption against a strong continuum source. This can be done in the UVIoptical
(e.g.. hot stars. Fig. 7.6) or in the infrared (e.g.. in evolved cool stars. Fig. 7.7). For

P
I I fi— 1— I I-
R 2 4 6 8
C IIIIIIII I I IIIIIIIIfI 1 I I I 1—-
J 64 2 0 26 I0l2

20 Aql

l l l I I l
4049 4050 405 l 4052 4053 4054
Wavelength (A)

Flg-ure 7.6
Electronic transitions of interstellar molecules can be detected in absorption againsl lhfl
continuum of background stars. This figure shows the rotational lines in the P. 9- "Id R
bands or the A'n, — X's; transition orc3 in the spectra of g Oph. ; Per. and 20 Aql (from
Maier et al. 2001 , ApJ. 553. 267).
 7.6 Electronic Transitions 205

c . . . . . s— , . . . ,

’ HPaschean . | '
to . l ‘ _. - l "‘ .

gnaw _
E _ i .
E _ _
g ‘l I l

E F
at: 0.6—- lI l | I i l .l _d
- l A
n a a 3 3 s 3 i
— . at! a: K it: 5': I .
-
A
to
a...
N V
H
O
A
N
6
v-
a
—-
3‘
- _
E: 356 as as 5 E5 E5
°""‘ 3§ s s52’
E E 52’
«:aE aE’ sE’ sE ‘'
. i ._ I _. i_ l . i i l

8740 8760 8730 3300

HA]

figure‘l’fl
thrationa] transitions to = 2 «— 0) of the Alli“ - X'Z; Phillips band of C1 in the Red
Rectangle observed with the 4.2-m William Herschel Telescope (adapted from Baltker et al.
1996. AM. 310. 893).

molecules that have nonzero L or S values (Sections 7.10.1 and 7.7.2. respectively),
weak Q branches (AJr = 0) are also possible.
When more than one vibrational—rotational transition between two electronic
states is observed. the line ratios can be used to probe the excitation conditions of
the molecules (Section 9.2). Figure 7.8 shows the optical absorption spectra of CN.
31". and CH. For the CH‘l' molecule. the fact that the R(0) line is detected. but not
the RU) line. suggests that the J = I state is not excited. Similarly. in the case of
CN, the fact that R(l), MO). and P“) are detected. but not R0), implies that the
J = l is populated but J = 2 is not. By applying an excitation analysis. assuming
that absorption of background radiation is the only excitation mechanism (Section
9.6). suingent temperature limits can be placed on the temperature of the background
radiation. Before the direct detection of the 3-K cosmic background radiation in the
millimeter wavelengths. the optical absorption spectra of light molecules was the only
probe of the cosmic background radiation.
Electronic transitions of molecules are rarely seen in emission in stars or in the
ISM. Absorption represents the cumulated effects of a column of gas between the
background continuum source and the charter (and therefore can be detected if
the column density is high enough). whereas emission requires a high volume density
of local gas. Other than in comets. where the electronic transitions of CH. CH+. and
206 lnrerstellar Molecules

{ A'l'l.v’=0
60 j.
40 q

"E 20
U
KJ :
so
v

B 1
zg=___.. .
z AIA' u’ = 0

.
-t

‘5
d-
20 T n
0.359rnm “i 1 i
O I 0.559“..-
I - _
in; v” = o 7 Kim. M = 0
LCD - “W m.“ - may! _
I I CIJHoJ “II- _|
R“)
0.90 - RI“) 4

0.80 - .1

' CN CH+ CH *
0.70 . 3(0) R 1( l ) .
1 _J l i l I"? l I . I i__nu.n\_L . 1 A 41 i
3872 3874 3876 4223 4230 4232 4299 430! 4303 4305
A (A)

Figure 1.8
Bottom: The absorption spectra of CN (left). CH+ (center). and CH (right) against 11 Oph. Top: The
energy diagrams showing the corresponding transitions. These light diatomic molecules can be used
as probes of the cosmic background radiation (figure from P. Thaddeus).

CN have been seen in emssion. there are only a few examples of electronic emission
lines. One such example is the Red Rectangle, where a number of vibrational—
rotational transitions of CN can be seen in the 322+ — x22+ transition (Fig. 7.9).

7.7 Effects of Nuclear Spins on Rotational Spectra

For homonuclear diatomic molecules consisting of two atoms of the same isotopic
nuclei (e.g.. H1. N2, 02). the Pauli exclusion principle requires that the overall
wavefunction be antisymmetric for a fermion (I is a. half integer) and symmetric
for a boson (I is an integer) upon exchange of two nuclei. The total wavefunction
is the product of electron spin. orbital, vibrational, rotational, and nuclear spin
 7.7 Efleccr of Nuclear Spins on Rotational Spectra 207

____,_1 r . . —r r I r . . r . . . I

1.04 — so) For 10 )2

*

4L
L5 14 13 I2 I1 l0 9 B 7 6 5 4 3 2 0 2 45s 7 9 ll

fl
l.02 '
-
IN!
l T I

l -.

é _-

E LOO -

E i
0.91! " '

0.96
i . _._ _._ . r .4. 4 . 4L 4 . . L r
3865 3310 3375 3880
Wavelength (A)

figure 1.9
m u = o 4 o vibrational-rotational transitions in the electronic transition band 322+ — x22+
of CN seen in emission in the circumsrellar envelope of the Red Rectangle. The narrow lines
(3(0), RU). P(l)) seen in absorption may be interstellar in origin. The strong absorption near the
fightedge is due to fly absorption at 3889 A (adapted from Hobbs et at. 2004. ApJ. 615. 941).

wavefunctions. The nuclear spin state with the larger statistical weight is called ortho
and the smaller weight is called para. The total wavefuncrion exclusive of nuclear
spin is labelled s for symmetric and a for antisymmetric. The selection rules are 3 4+ 5
and a 4+ a. effectively separating the molecule into two species. Since the rotational
wavefirnctions are antisymmetric or symmetric. depending on whether J is odd or
even. the nuclear spins determine the allowable values of J and. therefore, split the
rotational spectrum into two independent groups.

7.7.1 Molecular Hydrogen

Since the H2 molecule has two identical nuclei. nuclear spin plays a role in the
spectrum of H2. The two nuclear spins can be either parallel (I = l. the ortho state) or
antiparallel (I = 0. the para state). Since each of the nuclei is a fermion (I = 1/1). the
total wavefunction (to...) must be antisymmetric upon exchange of the two nuclei.
Since it.“ is symmetric because the nuclear separation is unchanged on simple
exchange of nuclei. and liter is symmetric for the ground state of H1. Wm must be
antisymmetric for ortho hydrogen and synu'nelric forpara hydrogen. Therefore. ortho
H; has only rotational states of odd J. and para H2 has only rotational states of even
J. In statistical equilibrium. the population ratio between ortho and para states is the
ratio of 2! + l. or 3 to l. The line intensity is proportional to the statistical weight,
which is 3(2J + l) for odd I and (2.1r + 1) for even J.1n the ISM. the H2 molecules
203 Interstellar Molecules

are predominantly in the lowest rotational states. J = 0 for para H2 and J

ortho H2.
The hydrogen molecule has two identical nuclei and has no permanent Electric.
or magnetic-dipole moment. The only observable transitions are elefll'iC-quadrupole
transitions. which have at} = -2. 0. and 2 (called 0. Q. and 5' branches, respec-
tively). The transitions are labelled as 0. Q. or S together (Jj). where JJ- is the l'Otation
quantum number of the lower state. Some examples of the vibrational—rotational m-
sitions of H; are ShOWn in Figure 7.10 and Table 7.4. Many of these lines have been
detected by ISO (Fig. 7. l 1).
Electronic transitions to the bound excited states 3 "E: and C '11., (called the
Lyman and Werner bands. respectively; see Fig. 7.1) occur in the vacuum ultravio.
let,l and such transitions of interstellar H; can be observed only above the Eanh’s
atmosphere. Rotational transitions in the Lyman band from interstellar Hz were lint
detected in absorption against the spew-urn of hot Stars by sounding rockets in 1910
and later extensively observed by the Copernicus and For Ultraviolet Spectroscopic
Explorer (FUSE) satellites (Figs. 7.12 and 7.13).
The excitation of the Lyman and Werner bands and the subsequent radiative de-
cays to high vibrational states of the ground electronic state can result in dissociation
(Section 14.2). Most of the time. however. the molecule falls back to a bound (1: < 15)
vibrational state and emits a series of infrared photons as it cascades through the bound
states in a process known asfluorescent radiation. The population distribution of H2
in various 1: and J states and line strengths of the fluorescent lines can be calcu-
lated using a procedure similar to that used for the recombination lines of the H atom
(Section 5.11).
In comparison with collisional excitation. radiative excitation by the absorption
of UV photons leads to large population of the upper vibrational levels, resulting in
relatively high fluxes in the lines with A < 2 pm. The different predicted line strengths
between thermal collisional excitation and nonthermal radiative excitation can allow
us to distinguish between these two mechanisms by infrared spectroscopy.
The 2.12] pm u = 1 - 0. J = 3 —- l S(1) electric-quadnipole vibration—rotation
line of H2 lies within the K band atmosphere window and therefore can be observed
by ground-based telescopes. When the vibrational state is excited either by collisional
excitation in shocked gas. or by fluorescent emission. this line can be seen in emission.
The 2.121-um H2 line is therefore useful as a probe of the dynamics or the radiation
distribution in interstellar clouds. In the absence of these excitation conditions. H;
can be detected in absorption against infrared continuum sources. and the v = l -+ 0
5(0) (2.22-um) and S( 1) (2.12-um) lines have been detected in molecular clouds
with embedded infrared sources. If the CO v = 2 -+ 0 vibrational bands are also
observed in the same sources. then the Hz to C0 abundance ratio can be derived.
This is particularly useful because when H: is not observable, CO can be used as the
tracer of the total molecular mass.

I. Vacuum qu-aviolet refers to the part or the UV region below 2000 A. which needs a vacuum in
the laboratory because of absorption by 02 in the air.
 “NE _________________________________ 4.48
36 .. _ J=3 Dissociation limit ‘

J: B
m __ — 1.0

—— J = 11

2—0 5(0) 4.695 |urn

1.139 pm

2—0 9(2)
1.242 mm

2~l 5(0) 5.053 pm

2.355 um
|'

2-1 5(1)
2.247 pm
5.511 pm
r
m _ -— 0.5
\-
6.109 ,um
1-0 0(2)
2 630 pm i

1—0 9(1) 6.910 pm

2 407 pm f

1—0 5(1) 3.025 ,um

2.122 ,um r

9.665 m
1—OS(2) _ r g
2.034 ,um \
\\. 12.279 ,urn
‘ \ ll'
\
“\\r #1035 pm
o ‘ \‘1 23.2!9 it rn o
v=2 v= l v=0

Figural“)
113° 9W diagram of molecular hydrogen plotted in columns of vibrational states. The rotational
SWFSm'Dni J=Olo ll inu=0. J=0I08 in u=l.and J=Ot03in u=23mploltcdas
hOI'Imnta] 1mm. Some of the 0. Q. and S unnsitions are indicated by dot-dash. dashed. and solid
lJI'm- Espectively.
210 Interstellar Ma19:21::

Table 7.4
Molecular hydrogen linw in [he infrared

(v1 — uJJAJUJJ Mum) £01,. 1;) (cm")

H, u = 0 -t 0
5(0) 28.21383 0.00
5(1) 17.03433 113.49
5(2) 12.27861 354.37
513) 9.66491 705.52
5(4) 3.02505 1163.31
5(5) 6.90952 1740.24
5(6) 6.10356 2415.03
5(7) 5.51116 3133.05
3(3) 5.05303 4053.51
3(9) 4.69461 5005.73
.500) 4.409 6039.15
501) 4.1313 7148.71
503) 3.3463 9530.75
H; u = 1 —D 0
3(0) 2.22329 0.00
5(1) 2.121113 118.49
5(2) 2.03376 354.37
3(3) 1.515756 705.52
9(1) 2.40659 113.49
0(2) 2.6269 354.37
0(3) 2.3075 705.52
0(5) 3.2350 1740.24
H2 11 = 2 —» 0
3(0) 1.189 0.0)
5(1) 1.162 1113.49
5(2) 1.1330 354.37
5(3) 1.1170 705.52
H; u = 2 —> 1
9(1) 2.5510 118.49
90) 2.5693 705.52
9(5) 2.6040 1740.24
 Table 7.4
(continued)

(3,. — 11.111111.) Mum) 5111.. 1,) (cm-'1

HID u 1: 0 -> 0
mm) I [.57346 4627.07
3(9) 12.47131 3325.27
11(3) 13.592155 3009.53
11(7) 15.25104 2423.33
11(6) 16.39331 1331.95
12(5) 19.43100 1317.31
11(4) 23.03376 303.10
3(3) 23.50197 532.31
13(2) 37.70155 237.07
R(D 5522975 3923
17(0) 1 12.07251 0.00
Uppcrsula: 17,-. J..L1wenu1:: 111. J}.

F I I l l l—T I A l I I I:|
Wm—flfs:
Wins sa: .1:1:; ex¢ 31: aa." -W ::

1000.0 3*anfifl mnnmuiiiiii

A g ? i 21 a21 1
figss’figg 5”: a;
3333333 I E j
g I_|! 1 ' 1 | A 1 1 .
i:- ‘°°-° 'é3. r'u'uf-
§§§ «'15 '3:
_2~ I 1 1 1 1-1' -
5 11“" II'll
; 10.0 11 I j
E E
“20 .
1.0 L —_
3 3
1-1,o—1u "‘ 2
OJ 1 1 1 |_ 1 1 1 J_ 1 1 1 I
2 3 4 5 10 20 30 40
Wavelet-011mm]
Flat-127.11
’50 SW39! specu'um of Orion showing a large number of H2 notational (u = 0 — 0. i — 1. 2 — 2)
Ind Wand—910121501111] (u = I - D, 2 — 1) emission firm. These lines represent gas excitation
“Emma ranging from 600 K to 3000 K (adapted from Roscmhal et at. 2000. AM. 356. 705).
212 Interstellar Molecules

E ..
fl _
= -.

E -

o . t l . . t l J . I . . . I . . -
1040 1060 1050 l 100 1120
Wavelength (A)

Figure 7.12
Many of theabsorption lines seen in this FUSE spectrum of the early-type (03.5 V) star HD 73382 are
from molecular hydrogen. The strongly saturated lines at M037 Aw = 0 — 5). 1.1049 Mu = 0 — 4).
nos: A(u=0—3). A1077 A(u=0—2),).1092A(u=0— 1),and).110a A (we—om: the
vibrational—rotational transitions arising from the ground rotational state Jj = 0 of the Lyman band
of H2. The higher rotational lines (JJ- = l. 2. 3. 4) are marked above the spectrum (adapted from
Ferlet 2000. ApJ. 538, L69).
gbhhbbbhh
OOOOOI—I—I—
Normalizedflut

1050 1052 [05-4 1056

Wavelength (A)

Figure 7.13
Vibrational—rotational transitions in the u = 0 - 4 Lyman band of H2 seen in absorption against a
hot star in the Large Magellanic Cloud ('LMC). Molecular gas along the line of sight in both the
Milky Way Galaxy (MW) and the LMC components is seen in this FUSE spectrum (adapted from
Turnlinson er al. 2002, ApJ. 566, BS7).

The distribution of H; can also be mapped by infrared imaging. The u = D - 0

5(9) 4.69pm pure rotational transition lies within the 4.8-um band of the Spitzer
Space Telescope IRAC instrument. Maps of the Galaxy in this band can therefore
trace the distribution of warm H2.
Of course. the abundance of H2 would be best inferred from its grouud'state I'D-
talional quadrupole transitions. for example, the para S(0) J = 2 - 0 and ortho 5(1)
J = 3 — lat 28.2138 and 17.0348 ttrn. respectively (Fig. 7.10). However. these emis-
 7. 7 Eject: ofNuclear Spin: on Rotational Spectra 213

sion lines are not accessible from the ground. and were only first detected by the 150
mission. When present. these lines represent the best means of direct determination
of the low-temperature molecular hydrogen mass in the ISM and galaxies. Even so.
we should remember that the 5(0)] = 2 — 0 line requires the excitation of the J = 2
rotational state, which is 500 K above the ground state. This large rotational energy
spacing is the direct result of the small moment of inertia of the molecule. At low
temperatures. molecular hydrogen is likely to be confined to the ground states (1 = 0
and l for para and ortho H2. respectively). and there is no emission mechanism that
can be used to determine the abundance of molecular hydrogen.
When one of the H atoms of molecular hydrogen is replaced by a deuterium atom.
the resultant molecule hydrogen deuteride (HD) is no longer homonuclear and there-
fore possesses a dipole moment. Several of the rotational transitions of HD (Table 7.4)
have been detected by [$0 in planetary atmospheres and the ISM. In particular. the
v = 0, J = l —a» 0 ground-state rotational transition of HD at “2.072 nm provides an
accurate determination of the abundance of HD and can be used to infer the deuterium
abundance. In warm molecular clouds where chemical fractionation (Section 9.10) is
not a factor and the HDsz abundance reflects that DIH ratio. this permitted line is an
excellent probe of the abundance of molecular hydrogen.

7.7.2 The Oxygen Molecule

The nuclei of the oxygen ("'02) molecule are identical boson particles (1 = O).
which requires that the total wavefunction be symmetric when the two nuclei are
interchanged. For the 31“.; gronnd electronic State. only rotational states with odd N
values are symmetric w. r.t. nuclear exchange and even N values are not allowed.2 So
instead of the usual two rotational ladders the oxygen molecule has only one. Due to
the AN 2 :l:l selection rule. electric-dipole transitions are not possible in the oxygen
molecule because the even N values are missing.
The oxygen molecule has two unpaired valence electrons and thus has a strong
electronic spin magnetic-dipole moment. The triplet symmetry of its ground state
(5' = l, L = 0) is manifested in the fine-structure Splitting of each N value (J =
S) into I — N. N :t 1. Levels of equal N are connected by magnetic-dipole fine-
structure transitions with d1 = :l:l (Fig. 'I'.l4). These lines occur at l 19 and 55—65
GHz and are responsible for the high telluric opacity at these frequencies. Levels of
differing N are connected by magnetic-dipole rotational transitions that have AN = 2
with frequencies in the submm region.
Molecular oxygen in the ISM has been searched for through the (N. J) =
3. 3 > I. 2 rotational transition at 43724938 GHz by both the Submiliimerer Wave
Astronomical Satellite (SH/AS) and the Odin satellite. The Odin satellite also has the
capability of observing the ground-state rotational transition of (N. J) = l. l —> I. 0
at l l8.75034 Gl-lz. As of 2005. 02 is yet to be detected in the ISM. with an upper
limit of N(02)/’N(H2) < 10".

2. For most molecules. L = O. S = O. t = 0. so the total angqu memenlum (J) is just the rotational
quantum number (N). However. in 02. S # 0. so N = J — S should be used to indicate the rotational
quantum number.
214 lmemeflarMolecules

6 -

— 1400

. 59-59
‘ ,o
5.5 60307 <
5.6 , 5.4
o {a
c, .' a.
s — 1200
I 0 V
," o' 1'
, .0 '1
r' 1' l _‘
..
,‘ ‘5' 1'
l‘ o. "
o' I.’ {I
I}? .- 1 1000
4 _ .u 1. "a .f

Equivalcm fleqnency (6H2)

A I f . .
:5 .‘ .‘ '99 If?
V - .' {1C5 .4
Q '. 0" fl 0'
g .' .' — two
I" o" o"
E 3 '— {l ”I. '0'
:3 o' o' 0' '
'l‘ 4" '0.

__ f u" I.

[—

— zoo

o o
J=N+l J=N JaN-I
Flam-e114
The energy diagram for molecular oxygen. The energy levels (horizontal solid lines) are Labelled
as N. J. The fine-strucmre lines are shown as solid lines whereas the rotational lines are shown as
dashed lines. Each transition is labelled with its frequency in GHz.
 7.7 Efl'ects of Nuclear Spins an Rotational Spectra 215

In the case of '60130, the molecule consists of two distinguishable particles.

which therefore breaks the symmetry. As a result, all rotational levels are present and
the molecule has twice as many rotational lines as I‘50'60 or H30'30. Since there
are half as many molecules in any particular rotational state, the rotational lines are
expected to be half as strong.

7.7.3 Hyperfine Lines in Molecules

As in the atomic case (Section 5.4). nuclear spin can introduce hyperfine splittings
in molecular transitions. For example. l“N has a nuclear spin of l. and the rotational
states of HCN are split into three hyperfine components (F :1 + I) F = J' — l. J, and
J + 1. For example, the J = l —> 0 transition of HCN has three hyperfine transitions
(AF=0.:l:l.F=J+I=2-> l. F=l—> Land F=0—> l).'l'herelativeintcn—
sities of these hyperfine transitions correspond to their respective statistical weights
of the upper states. and have values of 5. 3. and 1, respectively. Because of its high
abundance and high dipole moment (2.98 debye. l debye =10'” esu cm). HCN is
a widely observed molecule in interstellar molecular clouds and the observed rela-
tive intensities of the hyperfine lines can tell us about the temperatures and optical
depths of molecular clouds. An example of the hyperfine spectrum of HCN is shown
in Figure 7.15.

0.7
LIISZ
0.6 —

0.5 -

0.4 -

0.3
TA' ('0

0.2

DJ

0.0

-O.l

—0.2 l l I _L r l r | l
~10 ’75 0 5 I0 is
visa (km s I)

Flsun 1.15
Spectrum “the HCN J = I —> 0 line in L1152 showing the three hyperfine components. The actual
Observed line strengths of the three components do not correspond to the theoretical values of 1:5:3
(data courtesy of Yong-Sun Park).
216 Interstellar MoleCules

Table 7.5
The observed hyperfine lines of N2H+

Transition Frequency (MHz)

JF.F2—o J'F.’F£ 101—» 012 931762650

121 —9 011 911719666
123—> 012 93.171776?
122—50” 93.173.4796
Ill—r 010 94.172.0533
112» 012 93.171.9168
[IO—.011 921.171.6210

From Caselli er al. 1995. ApJ. 455. L77.

Although molecular nitrogen (N2) is a nonpolar molecule with no allowed

electric-dipole rotational transitions. it can react with H; to form the molecular ion
N2H+. which can be used to trace the chemistry of N2. N2H+ (diazenylium) is a
linear molecular ion (Section 7.l I) that was first detected astronomically before it
was studied in the laboratory. Coupling of the rotational angular momentum with the
nuclear spin of the outer N nucleus (the N at the end) leads to hyperfine compenems
F. =J+I.. Since I. = I (Table A2.2). F. has values of 0. l, or 2 for J = land a
value of 1 for J = 05ince F. = O is not allowed for J =0. For the J =1—> 093.174—
GHz rotational transition, the hyperfine lines term a triplet of F. = l —> I. 2 -> 1, and
0 —> 1 over a frequency range of ~ 4.6 MHz. Such small splittings are difficult to ob-
serve in a laboratory setting because of pressure broadening. But in a cold molecular
cloud. these hyperfine lines are easily observed. The hyperfine molecular constants
of this molecule are therefore best determined by astronomical means.
Each of tlte hyperfine components is further split by inletactions with the nuclear
spin ([2) of the inner N. The total quantum number is F2 (F2 =F.+lz) and has values
of 0. 1.2. or 3 for J = l, and values of0. l. or2 for J = 0. This results in a total ofseven
hyperfine components with separations of the order of ~ 0.2 MHz (see Table 7.5).
These hyperfine lines have actually been spectroscopically resolved in the spectrum
of LlSlZ.

7.7.4 Isotopologues of CO
Since some isotopt: of C and 0 have nonzero nuclear spins (13C. 1’ = 1/2; ”0.
l = 5/2, Table A2.2). hyperfine structures of the isotopologues of the most widely
obServed moleCule C0 can be detected in the lSM. For example. the lowest uansition
(J = l —r O) of C'TO is split into three hyperfine components as a result of theeleetrit:
quadrupole interaction with the l = 5/2 nuclear spin of '70. The hyperfine states
associated with J = 1 are F = 3/2. 5/2, and 7:12. and for J = 0. F = 5/2. Therefom
the possible hyperfine transitions for J = I -) Oare F = 5/2 —> 5/2. 3/2 —'> 5/1“"d
7/2 -> 5/2 (Fig. 7.16).
 I I 17 I l I I fii I r I
3|—

I
"""" ”0’0 (1 -—) 0)

IIIIII—IIIIIIII

I
_”C”0(l —> 0)): 20

I
l
I
I
:5,

I
I
a F = 50 —> 50 ‘3:

I
i: _=': 5

I
1 s ' 3!: —> 512

I
l
F»)
5-.
--.I

Ln
is
1.
II

L l
T; (K)

....... jzclgo (1 _) 0) _

_'3C'50 (l —)0) x 20
II_I_I_I

f5.
nu n
T“ (K)

I_Ll_l_lll
h

ll

Velocity ('kmis)

Figure 7.16
Swedish-E30 Submillimerer Tetacope (SEST) spectra of p Oph showing the J = I -> 0 (top)
and J = 2 —> 1 (middle) rotational transitions of c'To. andLhe J = l —> 0 msition of ”C'Bo
(bottom). Also shown are the expecled positions and rclalive strengths of III: C170 hyperfine
transitions (adapted from Bensch e: at. 2001. ApJ, 562. L135).
213 Interstellar Molecules

For J = 2 —+ 1, nine hyperfine components are expected, namely, F = 9f2 _,

7/2. 7/2 —+ 1/2. 7/2 —> 5/2, 5/2 —> 7/2, 5/2 —> 5/2. 5/2 —> 3/2. 3/2 4 5/2. 3/2 -+
3/2, and 1/2 —. 3/2. For ”c170. the nuclear spin (1 = 1/2) of 13c introduces mm“
splitting. but the splitting (~ 50 kHz) is smaller than can be observed with Prestem
spectrometers.

7.8 Rotational Spectra of Symmetric Tops

A molecule with an axis of rotational symmetry with two equal moments of inertia
is referred to as a symmetric top. A linear molecule is a special case of a symmetric
rotator where the moments of inenia along its molecular axis (1“) are very small and
the two other moments of inertia (13 and 1,3) are equal. To generalize from a linear
molecule, we can have a prolate symmetn'c rotator with an elongated shape Similar
to a cigar. The moment of inertia [,1 along the molecular axis of the almost linear
molecule is smaller than the other two (IE = Id. In the other extreme. we have the
oblate symmetric rotator (similar to a pancake) where [A = 13 4. 1C.
The corresponding rotational constants (see eq. 7.6) are defined as

C= . (7.18)

SincelA 515 510142320

The rotational levels ofa symmetric top are deseribed by two quantum numbers I
and K , where J is the total angular momentum quantum number and K is the angular
momentum projection onto the axis of symmetry. Since K is a component of J . it has
integer values —J. —J' + l, . . . . J — l. J. However. since the rotation energy of a
symmetric rotator is the same for clockwise or counterclockwise rotation. the K and
K states have the same energy and there are Only J + l K states for each 1.3 The
rigid rotator energy levels are given by

E” = 310' + 1) + (A — ELK: prolate top

= 31(1 + 1) + (C — B)K2 oblate top. (7.19)
Since A 2 B. the energy of a given J increases with increasing K for a prolnte EDP
while it decreases with increasing K for an oblate top (3 a C) (Fig. 7.17).
The electric-dipole selection rules are AK = 0. AJ = 0. :l:l. Since transitions
between different If states are forbidden, it is useful to write the energy diagrams in

3. Because of this degeneracy, K is sometim used for the magnitude of the projected £08111”
momentum and a separate symbol k is used to designate the value of K with a sign.
 7.8 Rotational Spectra afSymmetn'c Taps 2l9

4*.
8"—
6 3-— .—
3"."-
74—4 B 8-— 3'—
8——

5——

1,__. 6" 7— 7— __
tip—— 1 7—— 7.—

6——
5*— 3'*-— 6— 6 6
6".
6“— 6—
5___ 4—
5___ 5- ” 5* __
3—— 5 5-— 5_
2—— 4— 4—— 4 __ 4 —
3—- 3-—-— 3___ 4
3——

2— 2— 2.—
l-—- 1——
o___

K=I0 2 3 4 K=O l 2 3 4

Figure 1.11
The energy levels of prolate (left) and oblate (right) symmetric tops arranged in columns of constant
K. Because 1 2 K. the lowest state ofeach column is J .-= K.

columns (also referred to as “ladders") of states with the same If quantum number
(Fig. 7.l7). For each column of constant K. the energy levels start from the lovvest
state J = K. in steps of one to J = K + 1. J = K + 2. and so on. Transitions will
occur only between adjacent J states in the same column. As in the linear molecule
case, the successive rotational transitions (J = l -s 0. 2 —> 1. etc.) are separated by
23 in frequency for the rigid rotator. Since AK 2 0. we can see from eq. 7.19 that the
transition frequency is independent of K. that is. the AJ = I transitions in different K
columns have the same frequencies (except for nonrigid rotators; see Section 7.8.2).

1.8.1 Ammonia and Inversion 'h-ansltions

The ammonia (Ni-l3) molecule is an example of a polyatomic symmetn‘c top molecule
that is widely observed in the ISM. As in the H2 molecule. the wavelunction symmetry
under the exchange of two of the time identical H atoms leads to the separation of
the molecule into ortho and para forms. The rotation of the molecule by 120“ around
the symmetry axis is equivalent to the exchange of two pairs of H nuclei. and it turns
out that the molecule is in amino form if K is a multiple of 3 (Fig. 7.18).
One interesting feature of the NH3 molecule is the inversion transition where
the N atom flips from one side of the plane defined by the three H atoms to the
220 Interstellar Molecules

_| _l' T _l_ 'I I 1

Rotational energy levels of NH3 1=6

6— ‘ SCI]

5 s
300— '—"— = 5_
_ 1—
9.. ‘400

5: s
5‘ 5
| 4 __ __

E 200' -_-— f: 4 _— NOE

ti 4 g
2 -_2m.
3 3
100- '— 3

2 2 ‘J 100
= 2_
.1.-- I A=orrha
—- : E: rd
0 Pa
0— 7.: ‘0
4| i J J I I l
K=0 K=l K=2 K=3 K=4 K=5 K26
A E E A E E A

Figure‘Mli
The energy level diagram of NH3 arranged in columns of constant K . Each of tltc rotational
levels (labelled with their J values) is split into two inversion states. The excluded inversion
states in K = 0 are indicated by dashed lines (adapted fi'orn Ho and Townes 1933. Annual Rev.
Am: Ap., 21, 239).

other side. like the flipping of an umbrella under a strong wind. This motion splits
each of the rotational levels into two. The lower state is labelled + or sometimes
s (for symmetric) and the upper state - or a (for antisymmetric). Because of their
small energy separations, the inversion states of low rotational levels can be easily
excited. The 23.6945-GHz transition between two inversion levels of the Jx = I 1
level of para-NH; is commonly observed in the ISM. Due to nuclear spin statistics
and symmetry requirements. the K = 0 ladder only has the inversion 5 state in odd I
and a state in even J. Consequently. there are no inversion transitions in the K =0
ladder (Fig. 7. l8).
Each of the inversion doublets is split into hyperfine components due to the in-
teraction between the electric-quadrupole moment of the N nucleus and the electric
field of the electrons (Fig. 7.19). Weaker magnetic hyperfine interactions associllfid
 7.8 Rotational Spectra ofSyrrmetn'c Top: 221

Basic quadrupole Magnetic hyperfine splitting

5P“‘““3 F = , Satellite lines
F Main lines IF. 1 1 Outer Inner
tI I It KHz
m em _

'
r—

2
D
1......
"r: VII “to Hit "Mir

1. I42 KH:
pal-“y - 06' M” 2 3% 135 RH:
- 0 93 MHZ 0 ”2
10- I2 :17 15
fill 913 III 4_Idt6
Theoretical transition ___ a \
intensities 0 Line identificzttion numbers
\\\ I \ ‘\\

l \\ 3 9 Is I?
5 7 [6 I3
E 1‘) 6 [1.11.13 I ah I
F5 1.0 0.5 0 —0.5 —1.0 -l.5
¢——- Frequency shift (MHz)

I I I j r I I I I I

A Ll34N .J
:5 0.6 -
5i 04 F _'
E
g 02 ... —I
g o
I II II II II
I l I J— I I I J I I I
-19 -I5 -I1 -7 —3 I 5 9 I3 [7 2|
Radial velocity (km s")
Figure 7.19
T°P¢ The (J. K) = (l. 1) state of NH; is split into three hyperfine components as a result of the
nuclear spin of N. The AF = :l:l leads to 5 allowed hyperfine transitions. Each of these hyperfine
components is further split by magnetic interactions. giving rise to 18 transitions. Bottom: The NH]
1‘1 spectrum of L134 showing the 5 hyperfine lines plus some of the stronger magnetic hyperfine lines
(Indicated by arrows; adapted from Rydbeck et at. I977, ApJ. 215, L35).
222 Interstellar Molecules

—ora

+015

309.91 GHz 305.73 Gflz

—OI'G

+Ol'3

Figure 7.20
The two ground-state transitions of ND3.

with the H nuclei further split these hyperfine states and introduce 13 magnetic hyper-
fine transitions. Both types of hyperfine transitions have been detected in molecular
clouds.
Due to the existence of a symmeuy axis in NH3. the molecule has no dipole mo-
ment perpendicular to the axis. From the selection rules for symmetric tops (Section
7.8). rotational transitions between different K ‘s are forbidden and rotational tran-
sitions occur down the K ladder between successive J’s (Fig. 7.18). Most of these
transitions occur in the far infrared and are difficult to observe from ground-based tele-
scopes. The ground-state lo — 00 transition of NH; at 572.49815 GHz was detected
in 1933 with the 1010.
Although the ground-state lo — 00 transition of NH, can be observed only in
space. the corresponding transition of triply deuterated ammonia (NDJ) has a fre-
quency of ~ 300 GHz and can be observed by submillimeter telescopes on the
ground. Because of the difference in nuclear spins between proton (I = 1:12) and
deuteron (I = 1). both of the inversion states are present in the K :0 ladder in
ND... Consequently, the ground-state transition of ND; is split into two components
(J = 1, K =0inversion+ —) J :0, K = 0, inversion —-. and] = 1. K =Oinversion
— —> J = 0, K = 0. inversion +) of frequencies 306.73 and 309.91 cm, respectively
(Fig. 7.20). The statistical weight due to nuclear spin for a symmetric top with lhl'fl
identical Bose particles (which applies to ND;) is '/3(2l + l)(2l + 3)(l + 1) forodd
J inversion level +feven J inversion level —. and #30! + l)(2l — l)! for even I
inversion level +fodd J inversion level —. The line ratio of the I; -> I; to 1'; —> 10'
is therefore W = 10. given that l = 1. Each of the two components is fur-
ther split by the I4N quadrupole coupling into triplets (F = l —> 1, F = 2 -> 1. flfld
F = 0 —> 1) (Fig. 7.19). with statistical weight ratios of ZF + 1: 3:5: 1.
 7.8 Rotational Spectra ofSynmern‘c Top: 223

Given the low abundance ratios of deuteron to proton. deuterated ammonia was
expected to be diflicult to detect. However. as a result of chemical fractionation
(Section 9.10). the abundance of deuterated molecules can be much higher than the
DIH ratio at low temperatures. Both doubly deuterated and triply demented ammonia
have in fact been detected in cold clouds.

7.8.2 Centrifugal Distortion

As a molecule rotates. it may suffer from centrifugal forces that result in changes
in the energy levels. As in the case of nonrigid diatomic molecules (Section 7.4). the
effects of centrifugal distortion in symmetric tops can be approximated by introducing
three cenmfiigal distortion constants DJ. Dg. and D1xi

if = 310' + 1) -— D,[J(J 4-1)]: + (A - am? — DKK‘ — DMJU +1)K2. (7.20)

Consequently. the frequencies of rotatiOnal transitions between adjacent .15 are de-
pendent on the value of K :

v(J +1. K —-> J'. K) = 230 + 1) —4o,u +1)3 — zomu +1)K1. (7.21)
Methyl cyanide (CHJCN) is a prolatc symmtric top molecule. As a result of
centrifigual distortion, each of the rotational transitions J + l —> J is split into J’
different lines corresponding to different values of K(s J). These splittings are
illustrated in the spectrum of NGC 6334 in Fig. 7.21.

)5..............
I CH,CN.J=12-m

1.0

8
s
"‘ 0.5

0.

2.205 105 2.206 to, 2.201 [0’ 2203 :05 2.209 10’
RestfrequencHMHz)

Flam-e71]
The spectrum of the J = 12 —2 ll rotational transition of CH3CN in NGC 6334. The six
components (from right to left) at 220.747. 220.743. 220.730. 220.709. 220.679. 220.641. and
220.594 Gl-lz. correspond to K = D. l, . . . 6 (from Thor'wirth 2:01.. in Galactic Star Formation
across the Stellar Mas: Spectrum. eds. J. De Buizer and NS. van der Blielt. ASP Conference
Series. 287. 257).
224 Interstellar Molecules

Each of these lines is further split by hyperfine coupling due to the nuclear Spin of
”NU: l).ForJ=0,F=J' +r=0+t=t,andforJ=1,F=1+1=o,1,°,1
From the selection rule AF = O, :t:l. three hyperfine transitions F = 1—) l. 2 _, l.
and 0 —r I are possible. Under LTE. the relative Strengths of these three hyperfine
components are proportional to the statistical weights of the upper states. or 325:].
These hyperfine transitions of CH3CN were first detected in TMCI in 1982.
Anether example of a symmetric top rotator with centrifugal distortion is methyl
acetylene (propyne, CH3CCH). For example. the JK = 20 -> in and 2' —> lI [mug
Lions at 34.183 GHz are separated by ~ 660 KHz. Both methyl cyanide and methyl
acetylene are widely observed in the [SM

7.9 Asymmetric Rotators

A molecule is an asymmetric rotator when none of its principal moments of inertia

are equal. In this case, K. the angular momentum projected onto the symmetry
axis. is no longer a good quantum number. instead, the quantities K I and XI,
correlating to the limiting cases of prolate and oblate symmetric tops. are used, and
the energy levels are designated as JK __K r inorganic asymmetric rotators commonly
found in the lSM include H20. 503, H28, NHZD. and so forth. Examples of organic
asymmetric rotators include methanol (CI-[3014), ethanol (C2H50H). formaldehyde
(HZCO), thioformaldehyde (HZCS). isocyanic acid (HNCO). formic acid (HCOOH).
methyl formate (HCOOCH3), and so on.

7.9.1 Formaldehyde
Formaldehyde (HZCO) is a near-symmetric rorator with two moments of inenia nearly
equal but much larger than the third. The corresponding rotational constants are
A = 23l,970.672 MHz, B = 38.336.0455 MHz, and C = 34.002.2034 MHz. The
small asymmetry about the C—0 axis causes a splitting of the rotational levels into
K doublets (Fig. 7.22). Since the two H atoms can have parallel or antiparallel nuclear
spins. formaldehyde can be in orrho or para states that can be treated as two distinct
molecules.
The Afi-cm (4830-MH2) I 11 — i ,0 transition of HICO was one of the first molec-
ular rotational transitions detected in the radio (in 1969). This line is always seen in
absorption. even in dark clouds where no source of continuum radiation exists. This
suggests that the molecule is absorbing the 3-K COSmic background radiation itself.
Since the excitation temperature of the line is less than 3 K, the line can be considered
as an "anti-maser," where the upper level of the transition is selectively depopulflled
(or the lOWer stare selectively over-populated) by a pumping mechanism. One of the
first pumping mechanisms considered was collisional pumping. When neutral parti-
cles strike the H2CO molecule along the molecule plane. the lower level of the doublet
at each rotational level will be favorably excited. Rapid radiative decays with AJ = I
will lead to the overpopulation of the l .. lower state and therefore a lowering of the
excitation temperature.
 7.9 Asymmetric Ratator: 225

0.002 |’

—‘—— 3l2

: 73.975
- 3o

E 301 I I 2H
v I I
3 0.0m - H.438: 1 2
5 __i—_i—__ u
| I
| I
| I
150.488 : :
; : 140.833
——-w—-—,
l
2.. :' :'
r -1 ”5.603 _._l._,_
: {4.330
: lll
i Ortho
'1— 1..I
I 72.833

o L 1 om
Pam

Figure 1.22
The lowest roIaIional states of para and anho HZCO. The numbeIs are frequencies of the
transitions in MHz. The splitting of the doublets in the ortho states are magnified and not to
scale.

7.9.2 The Water Molecule

Although the water molecule has an axis of symmetry. its moments of inertia about
the three principal rotational axes are all different. with corresponding rotational con-
stants of A = 835,839.10 MHz. B = 435341353 MHz. and C = 278.139.326 MHz.
The water molecule is therefore an asymmcu'ic rotator and has a more complicated
rotational spectrum than symmetric rolators.
Figure 7.23 shows the energy diagram of para (I = 0) and anho (l = 1) water.
Each of the rotational quantum numbers J is split into 2.! + 1 levels. These levels
are described by two additional Iabets‘ L. and Kl, where L, = 0. . . . J and

4. K_, and X, only become quantum numbers in the limit of syrtu'neuic top.
 .55 2.533 I203:
gaggeflqaiuah .532...“ csnpaasnfi 3 32235235 In" 3 Euoflfisfiizgvfiagia
2:. .8 u .23 5.3 w 2. EE. “SEES 332: 5352 an... 2.8 $1-: a REE a. 295. 3552:. .32“ 53 S Sofia:
5.5 m=§_ E559 9: a o u i 5.5 35$ 5. .3 9530 a Buggs 23: 93a 2... Eu: ER... am. his 2F
mu. 2.5....
.2. 5.9
Se 8...
8... 8.:
3.0
3.9
8.:
3.:
8... 8.:
.55 8.0
mod 3.:
So 8.:
2... 2.9
93m
 7.9 Asymmetric Rotators 227'

XI = J _ K40: Kl: J -— K_. + l(exceptwhen K_.=D,then K. = J - K_1).lf

we denote + and —- as the evenness or oddncss of the K_. and K1 quanuim numbers,
then K4. K1 must be +— or —+ for artho water. and ++ or -— forpara water. For
example, the only allowed state (112.1.) for J = O is 000 and it is a para state. For
1 :1, K__. canbeOor l and the allowed states are 1m- 110. and l“. The first twoare
ortho states and the last one is a para state. The total number of states for J = l is
3, as required by 2.! + 1. For J = 4 the allowed states are 414, 423. 432, 4." for onho
water. and 404, 4.3, 422. 43., 440 forpara water. a total of2(4) + l = 9 states.
1heselectionrulesare A] :0. ii and K4. XI = ++ 4+ -- and —+ 4+ +—-,
so there is no cross transition from on‘ho to para or vice versa. As a result. these
two states of water can be treated as two separate molecules. These selection rules
allow transitions down each J ladder (e.g.. 432 — 423 where AJ = 0. as indicated
by lines without arrows in Fig. 7.23) as well as transitions to the next ladder (e.g.,
s31 — 44., where [U = l. as indicated by lines with arrows in Fig. 7.23). Most of
these transitions are in the far infrared (Table 7.6). Figure 7.24 shouts examples of
some of these transitions detected by ISO. However, sometimes two states in adjacent
ladders can be very close in energy. and the transition can occur in the radio region
(e.g.. the 6“, — 523 at 22 GHz). When the upper state (c.g.. 6.5) is at the bottom
of the ladder, molecules often accumulate in those states. resulting in a population
inversion (nigj/nJ-gi > 1). From eq. 5.15. we can see that the absorption coefficient
becomes negative under such conditiom. which implies that the optical depth is also
negative. This results in an exponential increase of line intensity with path length,
as each stimulated absorption will induce further stimulated emission leading to a
maser. This phenomenon. known as masing, makes the intensities of the lines much
stronger and therefore much easier to detect. The radiation transfer problem for water
is particularly challenging because the ground-state transition is highly optically thick
and there are many masing transitions (1' < 0).
After H2 and CO. H20 is often believed to be the third most abundant molecule
in the ISM. Because of the water content in the Bank's atmosphere. radiation from
cold celestial water sources is heavily absorbed by the atmosphere. As a result. the
abundance of water molecules is difficult to determine. Although 0 is the third most
abundant element in the Universe, the relative fractions of 0 in ionized (e.g.. 02+.
05+), atomic (0 I), molecular (H20. 0;), ice (e.g., water ice. C02 ice). or solid (e.g..
silicates) forms are net clear.
Historically, extraterrestrial water was first detected in the radio via its maser
lim, and in the infrared via its highly excited vibrational lines (“steam bands").
With the deployment of space-based telescopes, pure rotational transitions of water
have been detected in the infrared by ISO in many late-type stars. The ground-
state artho rotational transition of water (1 .0 - 101) at 557 01-12 was detected by the
SWAS satellite in dark molecular clouds and star formation regions. as well as in the
circurnstellar envelopes of the evolved stars.
The photospheric spectn of brown dwarfs (spectral classes “L" and “1”) show
prominent hot water bands. Although the Sun’s photosphere is too hot (7' ~ 5300
K) for water to exist. highly excited water lines are found in the spectra of sunspots
12.8 Intersteflar Molecules

Table 7.6
Rotational unnsitions of water in the fa: infrared

Species Transition Mum) Em (cm-'1

p-Hzo 5,. — 4.... 19.2300 222.05

o-H.o 55.. — 41. 22.6391 300.36
611.0 5... — 4.4 25.9402 224.34
611.0 4.... — 3.3 23.9133 142.23
64-120 7... — 6.. 29.3363 447.25
p-Hzo 5..2 — 4.. 29.3349 275.50
0-H20 4... — 3.. 31.7715 173.37
15-1120 5..1 — 4... 35.4710 222.05
614.0 4... — 4.4 37.9339 224.34
D-H20 6... — 532 40.3367 503.31
641.0 432 — 3... 40.6904 136.76
6.1-1.0 5., — 4... 45.1112 224.34
15-1110 33. — 2... 46.4335 70.09
p-HZO 4,... - 4.3 47.0235 275.50
611.0 53.. - 4., 47.9723 300.36
p—HZO 4...J — 3,. 49.2303 235.22
6.1120 4... — 3... 49.3357 235.42
21120 43. — 3.; 56.3242 206.30
p-Hzo 4n - 3.J 57.6361 142.23
611.0 432 — 3.. 53.6932 212.16
611.0 4.. — 4.... 61.3034 222.05
p-Hzo 3.... - 7.. 63.4570 536.43
0-H20 3... - 22. 66.4372 134.90
p-H20 3.. — 2... 67.0336 136.16
o-H20 3... — 3.,3 67.2639 136.76
p—Hzo 5.. — 4.. 71.0662 275.50
u-Hzo 7... — 6... 71.9460 447.25
0-H20 3.. — 2.2 75.3304 79.50
o-H20 42J — 3 .2 73.7414 173.37
o-H20 6... — 5.... 32.0304 325.35
p-HZO 6m — 5. 5 33.2331 326.63
p-H20 32. — 2.. 39.9373 95.13
p-Hzo 5., — 40. 95.6263 222.05
o-H20 so. — 4... 99.4924 224.34
 7.9 Asymmetric Roman- 29

Table 7.6
(continued)

Species Transition 11mm) Em (cm-l)

0-H20 5... — 4—... 100.9127 300.36

611.0 2... - 1.. 100.9023 37.14
euro 2... — 1.. 102.004 36.75
o-Hzo 2.. — 1... 103.0730 42.37
6.1-1gflo 2.. — 1... 109.347 42.02
o-H20 4.. — 3..3 113.5366 136.76
6.11.0 7.. — 643 1 [6.7836 85.63
311.0 432 — 4-.3 121.7191 300.36
p-HZO 4... — 3 .3 125.3534 142.20
611.0 3.. — 3.z 126.7126 206.30
411.0 4-13 — 4..l 132.4070 224.34
0-H20 5.. — 5... 134.9346 325.35
61-120 3..J — 3.. 136.4944 212.16
pnzo 3., - 2.... 133.5272 70.09
p-H20 4.3 - 322 144.5131 206.30
61120 322 — 3.J 156.1930 142.28
p-H.0 3.. — 4... 153.3090 222.05
6.1-1.0 3..3 2.2 174.6264 7950
0-H20 2.1 — 1... 179.5265 23.79
614.0 2.. - 2.. 100.4300 79.50
angst) 2.1 — 1... 1111.051 23.76
p-HZO 4.3 — 4.... 137.1104 222.05

(T 2 3000 K). Water emissions in bath infrared and millimeter wavelengths have
been detected in comets as their icy surfaces are being vaporized by sunlight.
Since the atmoqahen'c opacity for the isotopic species of water is lower. it is pos-
sible to study the low~level themal transitions of these species from the ground. The
2.3 —) I” (848.9619 GHz) and 1“ —> 000 (393.633? GHz) transitions of deuterated
water HDO were first detected in Orion KL by the 10.4-m Caltech Submillimerer
Tam-cape. Due to the nonmasing nature of these lines, the abundance ratio of l-IDO
to H20 can be detennjned accurately, and therefore can be used to test the model of
deuterium enrichment (Section 9.]0).
230 Interstellar Molecules

'2 fill—IIIIIIIWTIIIIITII _I— I I | i I l I l I I '__.__

— o-l-lzo
l0
F400“9 W um2 ,um ')

l lll‘llll
—C0]7-16
0‘

l
7.

I20 140 160 no

Mam)
Figure 7.24
Rotational transitions of water in the spectrum of the late-type star W Hya as observed by ISO LWS
(adapted from Barlow er al. I996. AM. 315, L241).

The high opacity of atmospheric H20 and 02 lines causes difficulty in observing
other molecular species with transition frequencies in the proximity of H20 and 01
lines. Some examples of such lines are l-l2D+ at! —-> 2|.2 at 1.112 TH: or 270 um).
Cl-I+ (J = [-9 Oat 336 GHzor 359nm), NH (N = 1—» 0, J =0-+ lat9460Hz
or 3'7 um). and Lil-l (J = l—> 0 at 444 GHz or 676 um).
Another asymmetric rotator that is similar to H20 is H2D+. While HZ; has no per-
mitted rotational transitions because of its symmetry (Section 8.2.1), its demented
isotopomer H2D+ has a large electric-dipole moment (~ 0.6 debye) and its rotational
transitions appear in the submm region. Specifically. the ground-state transition of
ortho HzD'l' (1.0 —- I“ at 372 (3112) has been detected in YSOs. The corresponding
ground-state transition of para HzD+ (to. —- 000 at [370 GHz) occurs in the vicin-
ity of strong atmospheric water absorption and is more diflicult for ground-based
observations.

7.9.3 Methanol: An Organic Asymmetric Rotator

Methanol (CH3OH) is an alcohol. which is defined as a compound that has hydroxyl
(OH) groups bonded to carbou atoms. Methanol has nearly the same geometry ‘5
water. with one H being replaced by a methyl group (—CH3). Since the methyl Group
has three equivalent H atoms, the combinations of the nuclear spins of these three H
 7.9 Asymmetric Rotators BI

fl----
Figure 1.25
Left: A schematic diagram of the methanol molecule showing the torsional motion of the
methyl group. Right: A projected view of the molecule with y being the torsional angle. (From
Xu. L.-l-l. 2001, in Spectroscopy from Space. Proceedings of the NATO Advanced Research
Workshop. eds. J. Demaison. K. Sarlta. and E. A. Cohen. Kluwer. p. 13].)

atoms create symmetry states called A and E. The A State corresponds to all spins
being parallel for a total of I = 3/2, while the E state has I = 1/2. The intemal
rotation of the methyl group against the HO—C framework is refined to as torsion
(Fig. 7.25).
Although methanol is an asymmetric rotatorI it is nearly a prolate symmetric top.
As a result, methanol energy level expressions can be approximated by eq. 7.19, and
its retational energy levels can be labelled by K . Figure 7.26 shows the rotational
energy diagram for methanol. Many of the rotational lines have been detected and
there an: 35] identified lines of methanol in the Orion specu'um shown in Figure 7.3.
Over 20 methanol rotational transitions have been found to be masers. For A-
methanol. maser transitions usually occur between the K = l and K =0 ladders.
whereas for E—methanol, most masers are between K =0 and K = —l ladders.
Examples of masers for A-methanol include 51 — 60 (6.7 Gl-lz), 3. — 40 (107 GHz)
and for E-methanol 20 -- 3_. (12.2 GHz) and the J; — J, series near 25 01-12 (see
Table 7.8).
Another molecule that is similar to methanol is acetone (CH3COCH3). which
has two identical internal rotors (two methyl groups attached to the CO group).
Consequently. the rotational specuum of acetone is complicated clue to interactions
between the two methyl tops with each other and with the rigid-body rotation of the
molecule. Each rotational transition is split into four components corresponding to
the products of A and E symmetry states of the CH3 rotors. Methanol and acetone are
among many asymmetric rotator organic molecules detected in the ISM (Figs. 7.27
and 7.28). Dimethyl ether (CH30Cl-l3) also has two internal rotors and each rotational
transition is split into four components as in the case of acetone.
232 Interstellar Molecules

l l 1 r i l __1____‘__.
20° lag—I4; _
35-8:
. - + + l0'-—IO'
”'2”: I3 '3‘ “Bu—133 12‘—12‘ s 5 7;---—7;
—_l4oo 1— I
1 7
.
II. 95 —95
p _
6‘ “6"
.3I=I3. izg—Iz; h— . .
150 _13. ' Iii—12; 7 , “3 ~85
['12- “1—“; lo‘_m‘ 7;--7;
'=I2'ii'—n'
. __12. ‘ 1 ’ ‘ 9;——9; tin-6,.
7A a1I'-==1|.'io,'—Io; 103—103 3.—3.' 5'—5*
’ ’
E
'3' ——11'0 9 J —-9‘3 -_ o- ‘
E 100 '01:"); 91—9; 87 ‘ 74 74

-Io,,' 9-'—91 fl‘-—3c "'" 6.—6:

5 L 1 1 7,-—7; sg—s.‘
e . v ’ °

“(—3:. 61—6; 5,—5; 72—7! 617—5; 4‘_4‘

t- _90
—-e; 7_
50 , ' 7- 52—5; 4,—4;
—-7n 6,'—— 6.’ 4;...4; 3, —3;
_6; 5|:— 5|: :2 :31.
‘5: til—41‘ z 2 :
4; 1,_.__3,_
—3u‘ 2I-_2i
-— . - I!

o [— 1:220.
De
" ' .
l 1 1 L 1 1 I
0 l 2 3 4 5 6
K

Figure'llls
The energy diagrams of A-methanol (above) and E—methanol (facing page) (adapted from
Val'lls er al. I999. Mon. Not. Roy. Ash: Soc. 310, 1077).

1.9.4 Cyclic Molecules

Cyclic molecules detected in the ISM include 3-membered carbon rings C3H and
C3H2. and ethylene oxide (c-C2H40), a 3-membered ring molecule and an isomer
of vinyl alcohol (CH2=CHOH). The most abundant ring molecule in interstellar
and circumstellar environments is cyclopropenylidene (C3H1). C3H; is a planar 3—
membered ring molecule (Fig. 7.29) with two hydrogen atoms attached to the ring.
Since the two H atoms attached to the two C atoms connected by a double bond
are equivalent. they create the para and arrha forms of the molecule. The quantum
numbers (J’Lh K!) of the rotational states. the separation of the rotational states into
onha and para groups, and the selection rules of the transitions are all very simililI “3
those of water. The two unpaired electrons on the third C make this an exccpfionfluir
 7.9 Asymmetric Rotators 233

I I I I I I I I I I I
' —-3 —l2 '
" ’ —l2.—”=—1I ’
no 9 ——-7, _
' —9 _ _ — a
_73 4 10" —12.
. —5 —1|1 _” ___uz_101 —6, -
.5 —8_‘ 3‘
" _9-3 _“0 _5s ‘
--54 —Il_.
lOOl‘ _74 _3 _1°" —tol —'02 —9, —74 '
‘3 —10n
" "—64 _7 _9-2
—m "I 9 _9 _33
_5‘ '
A
- _ ._5_‘ -3 — I I _5‘ .
E 4 6 9 —9° "‘7 4
g _ «I -J —B_1 — 1 _al —Bl I ‘ —

g _ —5.. _7 __
_80 —6. _
l-I-l _4_) -1 34 —7l _7: -5

50 — _3_I —6 —7D ’ ‘
I '1 —7-. —6l —6, —4, _
—5_ _60 _ _3.i
_ I —6_. _5t 51 _
_:'3 5 _sn _4. —42
_ :2: -| _40 —3| _31 _.

—'4-| —3tt —2| —2:

- _3-| _] —]I -
o_ _2_l
_._I = 0..o _
I I I I I I I | l |
—5 —4 —3 —2 —l 0 l 2 3 4 5
K

Figure'L26
(continued)

polar molecule (,u = 3.43 debye). The ground-state 1.0 — lo. transition ofonho-C3H2
(v = 18.343 MHz. .1 = 1.6 cm) is one of the strongest interstellar molecular lines at
short crn wavelengths. The counterpart of this line in water. a much lighter molecule.
is at 557 GHz (Section 7.9.2).
Generally speaking, small rings suffer from internal strain and are not expected
to be stable. C3H2 is able to offset some of this strain energy through the delocation
ofthe electron density.
The detection of these ring species raises the possibility of the existence of other
biochemically important ring molecules. Planar rings containing other heavy elements
(N, 0. S) in addition to C play a fundamental role in biochemistry. Examples of such
rings include furan (C4H40), pyrrole (C4H5N), and imidazole (C3H4N2). These are
234 Interstellar Molecules

'__l'—

5n
0.4- g
n 5I ..

an
A - I... Enm an E;

35‘; E“ is o“ 5 6n 5
E"0.2— u" 0::
n 0
UI I l =U!” 5n 5" |_
l r. O
3 =
n 8
=
U
6I
I
T 55 En i! I
I” l a

. . 1—; L I - l I_L - n I I I_l -_| u 1—- . L

ISL3 I51.4 l5l.5 lSl.6 151.7 |51.3 15L9

Rest frequency (GHz)

Figure 7.17
A sample specmtm of molecular hot core G327.3-0.6 from the SEST spectral line survey. Rotational
transitions of a large number of asymmeuic organic species can be seen. Approximately one-half of
the lines (unmarked) are unidentified lines (from Gibb er al. 2000. ApJ. 545, 309).

S-membered rings with one 0 atom (flu-an). one N (pyrrole), and two N (imidamle)
atoms as members of the ring. Furarl forms the basis of simple sugars ribose and
deoxyribose. the backbone moleules of RNA and DNA. Pyrrole forms part of the
amino acid proline and is a constituent of hemoglobin and chlorophyll. lmidaaole
forms a side chain of the amino acid histidine and the biomolecules histamine and
biotin. The N-containing aromatic compounds pyrimidine (c—C4H4N1) and purine
(c—C5H4N4) are both planar molecules where N atoms have replaced C in the rings.
They are the parents of the bases that constitute structural units of DNA and RNA-
Pyrimidine is the basis for cytosine (DNA and RNA), thymine (DNA), and uracil
(RNA). whereas pun'ne is the basis for adenine (DNA and RNA) and guanine (DNA
and RNA). Since these ring molecules are simple, their rotational constants can ht
determined from laboratory measurements. making possible the search for these
molecules in the ISM.
 7.9 Asymmetric Rotators 23S

I I I I— I I I
Sgt'BZfN)

E
0.50 r— o"
8:? ((31.13)2 C0 _
=
U

0.4-0 -
I :5. II II
.
<
_.
Q E 3.1 § <
L’- 3 3 23 ‘3
Zn r- r- r- r- r- =
U Ir: If: Ih. Ir: Ir: 0
A 0.30— I m' (Juana-no" I” In _
5 I g : on R g
. a . l": I i".
i- 3 3' U 8
D D in D :E
0.20 — I —

0.10 - I‘ _

I M
0.00 — _

| I I I l | I
91.528 91.563 91.603 91.643 91.688 91.723 91.763
Rest frequency (MHz)

Figure‘ms
NRAO Kitt Peak 12-m spectrum of Sgr 132 showing the rotational transitions of meiotic. The
notation B” - 8,5 stands for the blended 8L7 — 82.5 and 32,1 — 3...; transitions. Each of these
transitions is split into four different (E. AA. AB. and EA) components. although the EA
and AE components are often blended. resulting in characteristic triplets observed here (from
Snyder et at. 2002.Ap1. 578. 245).

c =C
/\
H/ \H
Figure 7.29
GeomeU'y of the cyclic molecule cyclopropenylidenc C3112.
236 Interstellar Molecules

7.10 Radicals

Radicals are molecules that contain at least one unpaired electron. Free radicals are
often highly reactive and unstable. However. some of the first interstellar molecules
detected are radicals (e.g.. 0H and CN) and many radicals are now observed in 5
9-C3H'
CCO, CH1CN,
Examples include SO. l—C3H, C4H, CSH. C6H. C3N. CCS.
and so forth (Table 7.7. Table A13). The existence of some of these lama}; was
never considered to be possible, and their detection was often the result of unbiased
spectral line surveys.
A radical with one unpaired electron possesses a net spin angular momentum
(S = I1'2). and the total angular momentum quantum number I = N + L + s can
therefore take on values of N :l: '12 for rotational quantum number N (for L :0)
One example is the CN radical (cyanogen). In the ground electronic state (X1}:+).
the unpaired electron splits the rotational states into doublets J = N :1: In, am
of the nuclear spin (1 = l) of the N nucleus. each of these levels is further split into
F = J' i ] hyperfine components. For the ground rotational state N = 0, J -_= 1/31
and the possible hyperfine components are F = 3f2 and F = 1/2. For N = l. J can be
3i: and Vi. giving rise to hyperfine components F = 5/2, 3/2. and 1i: for J = 3/2, and
F = 312 and '12 for J = In. There are therefore a total of 4 + 5 = 9 allowed hyperfine
transitions in the N = l —> 0 rotational transition (Fig. 7.30).
Another example of a free radical is C4H, which was first detected in space before
being studied in the laboratory. The observed doublet structure of different rotational
transitions of this radical allows the rotational constant to be determined. assuming
that it is a rigid rotator and has an electronic ground state of 1): l . Due to the nuclear
spin of the proton (I = 1/2), each of these levels is further split into two. corresponding

Table 7.?
Electronic ground states of
some radicals detected in space

Radical Ground state

CN 12+
so 31:-
l—C3H 2[1
cm 12+
C5H 211
C611 211
CJN 32+
cos 3i:-
cco 3:-
 7.10 Radicals 23?

1-3 ' t ' t ' I ' t ' l I

lrlll‘llllllllll]ll|l

iltltlililr_l_il_tlil.l
1.5 J=3I2—i 112

1.4 CNN=1—sO

1.2

1.0
A03 J=lr2-a|12
e
t: 0.6
0.4
0.2

0.0

—0.2
_l_ _l l I I I I I l I I

113.0 113.1 113.2 113.3 113.4 113.5 113.6

Frequency (GHz)

Flgure 7.30
The spectrum showing the hyperfine transitions of the CN N = l-r 0 rotational transition
in DR 21 obtained at the Onsala Space Observatory. The lines are (from left to right):
.1 = U: -> I12. F = ‘12 -+ 1:1, F = 1-! —r 312, F = 3:1 —> IE2. F = 3f: —> 3/1, and J = 3n —>
1:2, F = 3!: -> 1/2. F =11 —v 3/2. F = '82 -’ 1‘2. F = 1’2 -—> 1'2. F = If: —> 3/2 (data courtesy
of Henrik Olofsson).

to F = J + l = J :l: 1/2 (Fig. 7.31). These hyperfine splittings are also observed by
high-resolution astanomical spectroscopy.
Similar rotational structures can also be found in polyacetylenio radicals such as
CGH and Cal-l, which have 211 ground states. Astronomical Spectroscopy therefore
provides a valuable tool for the study of unstable molecular species that cannot be
measured easily in the laboratory.

7.10.1 OH
The ground state of OH is a 11 state (A = 1). Due to the presence of an unpaired
electron with S ; lI2. the spectroscopic notation of the ground state is 1113/1.” The
total angular momentum quantum number J (J = N + L + S) can therefore take on
values of 3f2. 5/2. 7f2. . . . for A + S = 3'2. and 1/2, 30.512. . . . for A + S = '1': for
rotational quantum numbers N = 0, l. 2. . . . (Fig. 7.32). When adopting this two-
ladder representation. one assumes a strong coupling between the electron spin and
the intemuclear axis (called Hund's case (a)). In fact, the states in the two ladders are
mixed and Figure 7.32 can only be viewed as a schematic representation.
238 Interstellar Molecules

N J F
SIZ —- 3
3 2

712 3
4

i
3f2 2
I
2

5/2

Figure 7.31
The energy diagram of C4H showing the electron spin and hyperfine splitting of the rotational
state N = 3 —> 2 and the four allowed hyperfine transitions.

The interaction of the electron orbital angular momentum and the rotational angu-
lar momennrm splits each ofthese levels into two states. called A doubling. The orbital
motion of the electron is doubly degenerate due to clockwise or counterclockwise mo-
tion of the electron around the molecular axis when A is nonzero. This degeneracy
is lifted when the molecule rotates. resulting in A doubling. It is analogous to the i-
type doubling introduced by the interaction between the rotation and bending motions
discussed in Section 3.1.
The interaction between the spin of the unpaired electron with the magnetic
moments of the nuclei further splits each A doublet into two hyperfine states (F =1 +
r, r = In for H, Table A2.2). For the ground state law. this results in four transitions
between the two A doublets for J’ = 3/2 (AF = 0. :l:l) at 1612.23] (F = 1 -> 2).
l665.401(F = l —> 1). 1667.353 (F = 2 —> 2), and [720.528 MHz (F = 2 -> I‘. see
Fig. 7.32). Because of the small energy separations between these states. population
inversion can occur as a result of infrared pumping to an excited rotational state of
OH. This leads to a negative absorption coefficient and maser action (Section 7.9.2).
Some examples of commonly observed interstellar molecular maser lines are listed
in Table 7.3.
Because of the high brightness of the maser lines. they can be mapped by
Very Long Baseline Interferometry (VLBI). which normally has surface brightness
sensitivities that are too low to map nonmaser lines. Very high angular resolution
images of maser emitting regions can now be routinely obtained by VLBI technin-Ifi-
Inter-ladder transitions are normally forbidden under Hand's case (50- However.
the 0H molecule is not strictly under case (a). and radiative transitions between the
ladders are permitted. The OH maser is pumped by absorbing a 34.6-irm photon
 7.10 Radicals 239

500 ___f 720

_ OH 2H —
+ -
. _ _ J31”. ..

400 - _ — 576
' "9n + + _ 55.23 pm ‘
. S:
L
q:
3.3-.
7
.

L €33 -

zoo -_ 55.39 pm o ' __ -+ '+ _

1-5/2 ‘. 432
- \5.“lu' ... ..

A \fgz' _- I
- _ '0. "I 98-74’Jm - Q

E, . + + ._ _-
5.13;"
a,
- I\
élfi'fl' J=7I2—_—-—_'- I“? + “233 L“
'5' _ _ J=3n _‘
-

. 161!me '
_ 34.4 _
_ + +
1: U2 _

m _ 1-512 _ In” - m
” F=2 '
- 119.44 mm F: 1 .
_ 16mm; _
was mm":
o - 1—3,: _ _ _ g=f _

. 2n = -

_ ”1 2n” J: 3/2 .

“m7.”
Ramaydiagnmforthe 0H molecule. The + and — notations reform the total parity ofthc A
emblem. which aiternatn with 1. 111: possible pumping (absorption) lines are shown as cloned and
m lines. and the downward cucadr. (emission) Iinos are shown as solid linw. '111.e four maser
Inn in the pound-state A douqu an: shown in an expanded diagram on the lowcr right (figure
w from Sylvesn'a er al. 1937. MNRAS. 291. L42).
240 Interstellar Molecules

Table 7.8
Examples of molecular masers observed in the ISM
__—--—.

Molecule Transition v(GH1) EMIHK) A(x‘l)

——-—..__
011 2113,21 =Jrz.F=1—2 1.612231 0 1.2911041
2(13‘.2.1=312.1=_—.1-1 1.665402 0 7.11:10-11
1n.,.1=7/2. F=2—2 1.667359 0 7.11 x 10-"
1173,27 = In. F = 2 — 1 1.720530 0 9.42 x 10-12
H20 11 = 0. 6... — 5;, 22.2350130 644 1.91 x 10-9
u = l. 440 — 533 96.261l6 3060 1.89 x 10"'
u = 1. 5... — 6., 232613670 3451 4.59 x .0-4
1.1 = 1. 1.0 — 1... 651100655 2329 5.70 x 10-1
510 0 =1. J = 1— 0 43.12203 1770 3.00 x 10-“
u = 1. J’ = 2 1 06.24327 1774 2.37 x 10-J
CH30H 42 — 4. 24.933468 45 8.40 x 10"
52 .. 5. 25.959030 56 3.74 x 10-a
s2 — 6l 75.010123 71 11.93 x 10"
Adapted from Mann. 1'. I975. in Frontier of Astrophysics. ad. E. H. Avrelt. Harvard University Pt'en. p. 385,

provided by dust continuum, and exciting the molecule from the ground 2[13,2 J = 3!:
state to 2n“2 J = 5/2 state (shown as a dashed line in Fig. 7.32). This is followed
by decays to 2n”. J = 312 (93.7 p.111). 2n”2 .1 = '72 (163.1 um). and 2am .7 = 312
(79.2 pm). A secondary pumping route is by stimulated absorption from the ground
state to 2n”. J = 372 (53.3 um) followed by decays at 163.1 and 79.2 pm. This
pumping mechanism is confirmed by ISO observations. where the 34.6-um line is
seen in absorption against the dust continuum in lRC+10420. and the downward
cascade lines (98.7. 163.2, and 79.2 um) are seen in emission. Some of these infrared
transitions are listed in Table 7.9.

7.10.2 CH
The CH radical is one of the first interstellar molecules detected through its optical
absorption Specmtm (Section 7.6). As in the case of OH. spin-orbit interaction of
the one unpaired electron of CH splits the rotational levels N into 2n”; and 211m
ladders (J=N+A+S,A= 1.3: 112,111: 1,2. .. .). AgajnasinOH.eachof
these I states is split into a A doublet (denoted by their parity + or —) and fulther
split into hyperfine components F = J + I (I = 1/2). In the ground state 1”172- “'3
aJIOWed hyperfine transitions are F = l - 0. 1 — l. 0 — 1 at 3349. 3335. and 3264
MHz. respectively (Fig. 7.33). The frequencies of the hyperfine transitions in the
This]: 7.9
0H lines in the infrared

9,. .+ a] 1,. p.- —+ 11.191 F,- —+ F}- Mum) Elm (cm-'1

112 .4 312 912 —+ 712 24.614 201.93

112 —+ 312 912 —+ 712 24.642 202.33
112 —+ 312 712 -+ 512 23.939 33.72
112 ..+ 312 712 -+ 512 23.940 33.92
112 —+ 312 512 ——+ 312+ 3 —+ 2 34.6034 0.06
112 —+ 312 512 ——+ 312+ 2 —+ I 34.6034 0.06
112 —+ 312 512 +-+ 312— 3 —+ 2 34.6294 0.00
112 —+ 312 512 +—+ 312— 2 —+ 1 34.6293 0.00
112 —+ 312 912 —++ 912+ 5 —+ 5 39.5139 355.12
112 —+ 312 912 —-+ 912+ 4 —+ 4 39.5144 355.12
112 —+ 312 912 +—+ 912— 5 —+ 5 39.6373 355.92
112 .+ 312 9n +- 912- 4 —+ 4 39.6330 355.92
112 —+ 3a 712 +—+ 712— 4 —+ 4 43.9497 201.93
112 -+ 312 712 +-+ 712— 3 —+ 3 43.9503 201.93
112 -+ 312 712 -——+ 712+ 4 -+ 4 44.0723 202.33
112 —+ 312 712 ——+ 712+ 3 —+ 3 44.0724 202.33
“‘2 —r JR 512 ——b 512+ 3 -> 3 48.7040 83.72
112 .. 312 512 ——+ 512+ 2 —+ 2 43.7044 33.72
112 -+ 312 512 H 512— 3 —+ 3 43.11163 33.72
112 —+ 312 512 +—+ sn- 2 -> 2 43.3163 33.72
312 —+ 312 1112 +—+ 912— 6 —+ 5 52.9339 355.92
312 —+ 312 um +—+ 912— 5 -+ 4 52.9333 355.92
312 —+ 312 1112 —-+ 912+ 6 —+ 5 53.0572 355.12
312 —+ 312 1112 -—+ 912+ 5 -+ 4 53.0511 355.12
112 - 312 312 ——+ 312+ 2 —+ 2 53.3513 0.05
112 —. 312 312 ——+ 312+ 1 —+ 1 53.3509 0.05
In —-> 3’2 312 +—r 3f2— 2 -> 2 53.2614 0.05
112 —+ 312 312 +—+ 312— 1 —+ 1 53.2616 0.05
112 —+ 112 912 ——+ 712+ 5 —+ 4 55.9497 429.47
112 -+ 1a 912 ——+ 712+ 4 —+ 3 55.9497 429.47
112 —+ 112 9r2 +-+ 712— 5 —+ 4 55.3903 429.47
112 —. 112 912 +—+ 712— 4 —» 3 55.3909 429.47
312 —> 312 912 ——+ 712+ 5 —+ 4 65.1315 202.33
312 —+ 312 912 ——+ 712+ 4 —+ 3 65.1314 202.33
3r: —+ 312 912 +_+ 712— 5 —+ 4 65.2733 201.93
312 —+ 312 912 +_+ 712- 4 —+ 3 65.2736 201.93

p, nl‘ers to 1511:1043! parity (+) or (—1 ol the A doublels.

Table 7.9
(continued)

9.- —> 521 1;. p, —r .11. pl- F} —> F} 101111) Elam: (cm—I)

112 d 112 712 --b 512+ 4 —> 3 71.170752 233.77

112 —> 112 712 ——> 512+ 3 —b 2 71.170350 283.77
m —+ m m +_» sn- 4 -» 3 71.215327 239.05
112 -’ 112 712 +-+ 512- 3 —h 2 71.215369 239.05
112 -> 312 112 --v 312+ I —> 2 79.117296 0.15
112 —+ 312 112 ——> 312+ 0 -—> I 79.113034 (105
112 —& 312 112 +—> 312- 1 —> 2 79.131726 0.00
112-. 312 112 +-r 312- 0—r 1 79.130923 0.1K]
312 —r 312 712 +-t 5f2— 4 —> 3 34.420391 33.93
312 —> 312 1/2 4—. 512- 3 —> 2 84.419938 33,93
312 —r 312 712 —-r 512+ 4 —h 3 34.596325 33.72
312 —> 312 712 -—r 512+ 3 —D 2 34.596312 33.72
312 —> 112 312 4—> 512- 2 —> 3 96.312205 33.92
312—b 112 312+—r 512- l —+ 2 96.313512 33.92
312 -b 112 312 ——> 512+ 2 —r 3 96.367469 33.72
312 —> 112 312 --b 5Q+ l -> 2 96.367404 33.72
112 —) 112 512 ——> 312+ 3 -> 2 93.724377 137.75
112 —b 112 512 ——> 312+ 2 —> I 93.724920 137.75
In -P 112 512 4—) 312— 3 -v 2 93.736390 137.49
112 —> 112 512 +-> 312- 2 -v- I 93.737035 137.49
112—» 312 512+—> 712- 3—! 4 115.1530 201.93
112 —b 312 512 +—> 712- 2 -> 3 115.1541 201.93
112 -> 312 512 ——r 712+ 3 —r 4 115.3353 202.33
112 —> 312 512 ——. 712+ 2 —r 3 [15.3390 202.33
312 —> 312 512 ——> 312+ 3 -—b 2 119234132 0.06
312 —r 312 512 —-h 312+ 2 —> 1 119232433 0.06
312 —r 312 512 +-+ 312- 3 —v 2 “9.441669 0.11}
312 —b 312 512 +—> 312- 2 —r 1 119439315 0.11)
112 —P 312 712 ——) 912+ 4 -) 5 134.3449 355.12
112 -r 312 712 --r 912+ 3 -> 4 134.3476 355.12
112 —h 312 712 +-> 912- 4 —r 5 134.9642 355.91
112 —I> 312 712 +—b 912- 3 v-) 4 134.9696 355.91
112 -b 112 312 +-b 112- 2 -b 1 163.124275 126.45
112 —- 112 312+—v 112— I -> 0 161122431 125-45
112 -D m 312 ——> 112+ 2 —> I 163.397176 126.29
112 -b 112 3B --> 112+ I —D 0 163.396W2 126.29

p, mfmlodctmal parity (+)0I'(-)ol'lhc 1'1 doublets.

 7.70 Radicals 243

CHFI'I

1251 + 2
3 2 + 1
4 5:2

2
1,a _ _ 2
S 75 180m '-'
E :E :‘E 203m 149.3911".
.3‘5 50- ‘3z 32 149.com nu
’5 l." r" ==£
a l _ 1 2:2
3 2 $33
nfigl
25-2 312
+
1 560mm '— .o
0" U2

+ 4-11
o
F F1 1 N J F, F
Figure 7.33
The lowest rotational levels of CH. The allowed transitions are indicated by at'rOWS (adapted
from Staeey er al. 1987, ApJ. 313. 859).

2113,: are F =2' -> 2". 1‘ —+ 1*. 1‘ -> 2+. 2‘ —+ l at 701.63, 722.1. 724.72.
and 704.27 MHz. respectively. The 3-GH2 transitions Were first detected in 1974.
and the 0.7-GHz lines in 1985. Because of the light weight of CH. its rotational
transitions are in the THz range. The N = 2 —+ l rotational transitions 2113,; —>2 ['11,2
at 149.3901tm (— —> +) and 149.091 ,um (+ —> -) (Fig. 7.33} were first detected in
absorption against Sgr BZ by the KAO in 1987.

7.10.3 SO
The short-lived free radical SO has the same electronic ground state as 02 (3):). Since
5 = 1. all rotational transitions are split into three levels with] = N + S. except N =
0 where J = S. The fine-structure lines (AN = 0. A! = it) are magnetic-dipole
transitions. whereas the rotational transitions (AN = :l:1. A] = 0. :l:l) are electric-
dipole transitions. Examples of rotational transitions of SO are (N. J) = 2. l —+ l. 1
(13.0437 GHz).5 0. l —> 1. 0 (30.00152 GHz). 3. 2 -> 2. 2 (36.20182 GHz). 1. 2 -;
0, l (52.93180 GHz). 2. 2 -> 1. 1 (86.09395 6112). 2. 3 —> 1. 2 (99.29987 GHZ).

5.111: energy level is sometimes Written as N; in the literature.

244 Interstellar Molecule:

25— __ 5.6
__4,4

20— “fir-4.3
F __ 45 3.3
315— '____,.e..- 3,;
g 2.2
s'=g 10 l— —— 3.4 —_ 1.1
Mum
G
3
2.3
5|-
__ 1.2
I on
\N
0- —i.o
J=N+l J=N J=N—l
Flgure1.34
The lowest rotational energy levels of 50. The labels are N , J as in the oxygen molecule
(Section 7.7.2). Solid lines are examples of the rotational transitions.

3, 2—+ 2, [(109.25222GH2). 3. 3. —> 2. 2(129.l3892 GHz). 3, 4 -—> 2. 3(133.l7360

GHz). 4. 3 —> 3, 2 (l58.9‘7l30 GHz). and 4. 4 -—> 3, 3 (17218146 GHz) (Fig. 7.34).
80 is the first molecule with 32 ‘ ground electronic state to be detected in Space
(02 remains undetected as of 2005). The rotational transitions of SO are very strong
and its higher transitions can be detected all the way to the submm (Fig. 7.3).

1.10.4 Methylene
Methylene (CH2) is an asymmeuic lop molecule with two unpaired electrons. [t has
an electronic ground state of 3B. and is the simplest neutral polyatomic molecule with
a triplet electron ground state (Section 7.2). Due to S = I. each of the rotation level
My ”(I is split into fine-structure stares of J’ = N — l. N . N + 1. Since each of the
two H atoms have a nuclear spin of I = l/Z. CH2 can be in either ail-tho (I = l) 01'
para (1 = 0) forms. For the artho form. each of the fine-structure states is funher split
into hyperfine states of F = J -— l. J. J + 1. whereas the para form has no hyperfine
splitting. Selection rules for rotational transitions are A} = 0, it and AF = 0. 3:1-
All ortho states have K_. + K; being even. and para States have K I + K1 being
odd.
 7. 10 Radical: 245

THO
Orrho Para
—- 250 K

4384 pm 4“
3”"
—— 200 K

2
" —— 150 K
153.35 pm 303

111
J-
316.96pm I00 K

202

[27.65pm -- 50 K

[01

0 JL.
on

Figure 1.35
low-lying rotational levels of CH2, showing the wavelength of the strongest tine-structure component
ft: each transition (adapted from Polehampton et aL 2005. AM. 431. 203).

The lowest rotational levels of CH; are shown in Fig. 7.35. All the transitions
are in the far infrared and not accessible from the ground (Table 7.10). The lowat
rotational transition observable from the ground is 40! — 3 13‘ with three rotational
transitions between the fine-structure components (J = 5 -— 4 at 68.37 61-12. J =
4 - 3 at 70.68 6112. and J = 3 -— 2 at 69.01 GHz). 111ese transitions. as well as
the F = 6 — 5, S — 4, 4 - 3 hyperfine components of the J = 5 - 4 transition, were
detected in Orion KL in 1995. The low-lying far-infrared transitions were detected in
Sgt B2 in absorption by ISO and will be observable by the Herschel satellite and the
Stratospheric Observatory for Infrared Astronomy (SOFIA).
The methyl radical is formed in the diffuse ISM through dissociative recombi-
nation of CHQ‘+ (Section 14.1). Both the methyl (CH3) and methylene (CH2) radicals
are important neutral building blocks of carbon chemistry (Chapter 14).
246 Interstellar Molecules

Table 7.10
Wavelenglhs of the lowest rotational
msitions 01' CH;

Transition A (um)

1.1-0.” J=0—l 12131450

1.1—0“, J = 14 12105023
1.1-0“, J = 2-1 12164614
211—20: J =1-1 153.102312
2.1—2.3 J = 1—2 154.302721
2.,-202 J = 2-1 152.621311
2.1—202 J = 2-2 151014101
2..-2(u J = 2-3 152992296
2. [-202 J = 3-2 154170941
2..—2¢.z J = 3-3 151352914
3l3-202 J = Z-I 93.5338
3.3—2.3: J = 2—2 94.0309
3|3-201 J = 2—3 93.723]
Elly-202 J = 3—2 93.7025
3'3-202 J = 3—3 93.3967
35-202 1 = 4-3 93.662]
l'o-IOI J = 0—] 15543947
1 .0—10. J = 1—0 155.66632
1.0-101 J = 1-1 157.56539
1.0-1”I J = 14 15616025
1.0—101 J = 2-1 157.12503
1m-1m J = 2-2 156.33233
2.3-101 J = 1—0 101.2941
212401 J = 1—1 100.1935
2.1.41Jl J = 1-2 107.0170
2.1—10. J = 2—1 101.0573
2.1-0J1 J = 2-2 107.4332
2W1°l J =3-2 101.7203
Table dnpwd from 961mm :1 4:11. 2005.
111174.431. 203.
 7. H Molecular Ian: 24"

”1 Molecular Ions
The molecular ion CH+ was among the first molecules detected in space. CH+ does
not have a suitable transition in the nun band. and it was first detected through its
electronic absorption band in the ultraviolet (Fig. 7.8). Because of its low molecular
weight. the rotational transitions of CH+ lie in the submm and far-infrared region.
The J = 2 -—> 1. 3 —r 2. 4 —+ 3 at 180. 120. and 90 .um. reapectively. were detected
by 50. When the Herschel Telescope is launched. the J = l—> O rotational tran-
sition at 359 um will also be observable. CH+ is an important signature species of
high-temperature gas chemistry (i.e.. shock chemistry). but not photon-dominated
chemistry at low temperature (Section 14.7).
Another interesting molecular ion is Hg" (Section 8.2.1). H; is the direct product
of cosmic ray ionization of H2 (Section [4.4). H; is highly reactive with othentvise
nonreactive molecules such as CO and NZ to produce HCO+ and N2H+:

H; + C0 —» 1100*“ + 1-12
H; + N2 —+ N2H+ + H2 (722)

(Section 7.7.3). H; therefore plays an important role in the destruction of C0 and

N2. H; is the key player in low-temperature ehernisuy in that it reacts with C. N, 0
atoms to put the heavy atoms into chemical circulation at low temperatures, as in the
reactions

N + H; —> NH+ + 1-12

0 + H3; —+ 011+ + Hz. (7.23)
Since CO is the second most abundant molecule (after H2) in the ISM. CO+ can
be one of the most important molecular ions. However. the high ionimtion potential
(14 eV. Table A2.3) of CO implies that it is difficult to be ionized in the diffuse
ISM where most of the Lyman continuum photons are absorbed by H. The most
likely places where C0+ can be detected are dense molecular clouds illuminated
by bright UV sources. Such as interstellar PDRs and planetary nebulae (Fig. 7.36).
With its relatively high dipole moment (2.771 debye). 00‘“ can be detected even
at low abundances. In the subnun region. there are several rotational transitions
available for observation. including N = 2 —> 1. J = 5/2 —> 3/2 at 236062553 GHz.
N=2—> 1. J =3/2-+ 1/2 at 235789641 GHz. N=3—>2, J=5/2—> 3/2 at
351741262 GHz. and N = 3 —+ 2. J = 7/2 -—> 5/2 at 354.014247 GHz.
C0+ can be produced through various ion-molecule reactions (Section 14.7).
It is destroyed by reaction with H and Hz to form C0 and HCO+, respectively
(eq. [4.49). I-ICO+ is a product of gas-phase ion—molecule chemistry, where the
chemistry is initiated by cosmic ray ionization of H2 (or other energetic events). It is an
immediate precursor of C0 as well as a product of destruction of CO (Section 14.1).
The J = l —> 0 rotational transition of the molecular ion HCO+ was first detected in
the ISM in 1970. Since this 89.189-GHz line has no known laboratory counterparts.
248 Interstellar Molecule:

HCO+(J=4—+3)

’. I'll-”(30* (J=4—v 3)

C0'(N=3—>2)(J=7f2—>5/2)

HCN(J=4—)3)
Tm (K)

CN(N=3—)2)(J=TIZ—>5f2)

' C1H(N=4—>3)(J=7/2-)5f2) :(J=9l2-—)7I2),' '

I

—l0
I3CO (1:3 —> 2)
J L
CO(J=3->2)

141; I
-50
VB“ (km/s)

Figure 7.36
The molecular ions HCO+ and CO+ in the PDR in the planetary nebula NGC 1021. Molecular
ions are important in the chemical networks of PDRs. More than 1?. molecules (someillusfltfld
above] have been detected in the molecular shell heated by a very hot (> 200.000 K) central
star. All molecular lines have similar broad profiles. suggesung that they originate in the same
region (adapted from Hasegawa and Kwok 2001. ApJ. 562. 824).
 7.12 Molecule: Containing Metals 249

the name X-ogen was first proposed as its molecular carrier. It was soon identified
with the previously unknown ion HCO+ based on its similar electronic configuration
with HCN. l-lCO+ (fonnyl ion) is extremely stable and is the most abunth molecular
ion in the ISM. In galactic molecular clouds. its abundance is as high as that of HCN.
CN. CS. and HZCO. With its charge and very large dipole moment (3.3 debye). the
rotational u-ansitions of HCO+ are widely observed.
Chemically. the formation and destruction processes of HCO+ are relatively well
understood. Physically, HCO‘ is often used as a probe of the physical properties
(dynamics, density. temperature) of molecular clouds. The presence of HCO+ in
space is a conclusive piece of evidence that (i) the gas-phase, neutral—ion reactions
(not grain catalyzed or thermal equilibrium chemistry in stellar atmospheres) are the
major chemical processes that produce observed neutral molecules in cold gas in
space; (i) atoms and molecules are very slowly ionized (probably by cosmic rays)
even in apparently neutral regions (dark clouds. circumstellar envelopes) in space;
and (iii) the gas density and ionization degree are sufficiently low that molecular ions
do not quickly recombine.

7.12 Molecules Containing Metals

Most known interstellar molecules are made up of abundant elements such as H. C.
N. and O: molecules containing elements in the lower rows of the periodic table are
much more rare. Among the possible candidates are molecules involving Na. Mg, Si,
P. S. and Cl. although only molecules containing Si and S are found to be common.
While Mg has similar cosmic abundance to Si. the nondetection of MgO implies that
the MgO to SiO abundance ratio is less than 10 3. Possible reasons for the scarcity
of these molecules include depletion into grains or that somehow chemisu-y does
not favor their formation under low temperatures. In molecular clouds. refractory
molecules are believed to be heavily depleted in the gas phase. and the only commonly
found species are SiO and SiS. However. in circumstellar envelopes, a much richer
variety of refractory molecules is found.

7.12.1 Halides and Cyanidec

A number of halides and cyanides have been detected in circumstellar envelopes.
Possible candidates for astronomical searches of halides include AlCl. AIF. NaCl.
and KC], and for cyanides or isocyanides, MgNC. NaCN. MgCN. and AINC. AlNC
is a linear molecule with a 'E* ground electronic state. Figure 7.3? shows the spectra
of four different rotational transitions of AlNC. The double-peaked profiles of these
lines suggest that the emission region is resolved by the telescope beam (Section
l5.7.2) and is extended into the outer regions of the circumstellar shell. The derived
fractional abundance of this molecule is f(AlNC/Hz) ~ 3 x 10'"). much lower than
the abundances ofhalides (f(AlF/Hz) ~ 1.5 x IO'T. f(AlCl/H2) ~ 2.2 x 10 ‘7).The
total abundance of aluminum in molecules is therefore only a small fraction of the
element. assuming that the cosmic abundance of Al (3 x 10—6) is applicable to the
circumstellar envelopes of AGB stars.
250 Interstellar Molecuies

AINC
‘lrfi.'-.J[r-‘I lRC+10215

“(L J=ll—le cuccs

0°03 .7. 14—— c,H—~ -

0.004

01MB
w - M w.
'

Sig—l 1:124“
\f

0.004

g
*5
‘u 100 WUWWN “f1 :13 —> 12 1—— Sig
0.003 L J, c,s_—.
u—9
0.004 A

0.000 - 1

J=|3-—DI7
0.010 — ”sscz—b ”SiC:—’ ‘
l
0.005 '- "

0.000 - 11 ‘
4—] l. A 1 n L l A . l 1 l

489 IOB —27 54 135

'I/LSR (km/s)

ngre7.37
[RAM30-mspectraoflRC+l02l65howingtheJ =ll-r [0.124 ll.l3-) lZ.andIB—b l7
rotational transitions of AlNC at 13], I43. ISS. and 215 GHz. respectively (from Ziurys “‘1‘
2002. ApJ. 564. L45).
 7.!2 Molecules Containing Metals 251

Since some transition metal elements (such as Fe, Ni, Cr, Mn, etc.) also have
high cosmic abundances. it is likely that molecules containing these elements also
exist in the ISM. For example, the nickel monochloride (NiCl) radical has a ground
electronic state of 2“3,; similar to that of 0H. and has rotational transitions in the
submillimeter region. The J = we — 341/2 transition of ”Ni-”Cl has been observed
to have a frequency of 385.719 696 OH: in the laboratory. The rotational spectra of
other transition metal carbides (e.g.. FeC. CoC. NiC, etc.) have been recorded in the
laboratory. Since the MC] molecule is highly ionic, most of the unpaired electrons
are near the Ni nucleus with neglible electron spin density near the Cl nucleus.
Consequently. the hyperfine structure is small and difficult to observe.

7.12.2 Calcium Carbide

Among the common metals, calcium is the only element with no molecular species
detected as of 2005. Since the cosmic abundance of Cu is similar to those of Al and
Na. the absence of Ca-bean‘ng molecules in the ISM suggests that Ca may be heavily
depleted in the gas phase due to condensation onto grains. One likely molecular carrier
of Ca is calcium mono-carbide (CaC). The ground electronic state of this radical is
31?. , which has two unpaired electrons giving a total electron Spin of S = 1. Each
rotational transition therefore has three fine—structure components. 1 = N — l. N ,
and N + 1. Laboratory measurements suggest a rotational constant of 10.338 Gl-lz,
giving rise to detectable transitions of N = 4 —> 3 and N = 5 —> 4 at 82.? and 103.4
GHz, respectively.

7.12.3 Molecules Containing PhOSphorus

Although phosphorus is the 17th most abundant element in the Universe (1 1th in
the Earth's crust), the only known astrophysical P-bearing molecules are PN and CP.
Since P is an important element in the biochemistry of living things, for example.
being involved in the storage and transfer of information (nuclei acids), energy transfer
(adenine and guanine nucleotides). membrane structure (phospholipids), and signal
transduction (cyclic nucleotides), the detection and abundance determination of P-
bearing molecules is of great interest. Possible candidates for future searches include
P0, P02, HCHP, HPnN. and so on.
11m ground electronic state of the PO molecule (le'l) has a spin-orbit cou-
pling constant much larger than the rotational constant, therefore only the lower fine-
su'uct'ure state 2n”: is 111:er to be populated. As in OH (Section 7.10.1). each to—
tational state J is split into two through A doubling. which is in turn split into two
hyperfine levels because of the nuclear spin interaction of 3' P (l = 1/2). The first ro-
tational transition lies in the u = 100 Gl-lz range and can be searched by min-wave tele-
scopes. Forexmple, the 2nm. J = 5/2 -+ 3/2, F = 3 —> 2. p = - -+ +, and F =
2 —> I, p = — —+ 4 transitions areat I08.998446 and l09.045396 GI-lz. respectively.
P02 has a very complicated rotational energy structure and the molecule is
spread over a large number of rotational levels (large partition function, Section 9.1).
Therefore the chance of detecting a particular transition is higher in a cold object.
where the number of populated levels is kept to a minimum.
252 Interstellar Molecules

The PH radical is another candidate for detection in the ISM. PH has an X3:-
ground state. and laboratory studies have placed the N = l — 0 transitions of PH in
the 423-554 GHz region and the N = 2 - 1 transitions near I THz; all are biockedb
strong telluric absorption. As both P and H possess individual nuclear spins of '12. the
hyperfine states of the rotation transitions can be labelled as F = F] + NH). when:
F1: J + l(P)and J = N+S.Sinee$= l. the N= [-0 transitionsofl’flh.“re
three separate components: J = D — 1. 1 — l. and 2 — l in the region of 423. 553, and
494 GHz. respectively. For the J = l — 1 line, the possible values for F1 are “2 and
3/2, and F = 0. l. and 2. The expected strongest transition of the J = l _ 1 lines is
F = 2 — 2. F. = 3/2 - 3/2 transition at 55336285 GHz. This line was searched by
the Odin submillimeter satellite in IRC+I0216 and was not detected.

7.12.4 Metal Hydrides

Since H is the most abundant element in space. metal hydrides are naturally elm
to be widely present in the ISM. Although the electronic transitions of Crl-I and
FeH have been detected in the atmosphere of late M stars. the rotational transitions
of diatomic metal hydrides such as NaH, OH, and Mgl-l have been searched far
without success as of 2005. The ground-state rotational transitions of these light,
fast rotators occur in the submm part of the spectrum (see Table 7.11). For exanrplc,
the J = 1 -—> 0 transition frequencies for 23Nal-l and 39KH are 289.864 and 202.282
GHz. respectively. Since both the Na and K nuclei have a nuclear spin of l = 3/2. the
J = 1 -> 0 transition of these molecules is split into three hyperfine components. F =
5/2 —> 3/2. F = 3/2 —> 3/2, and F = 1/2 —+ 3/2 (Section 7.7.3). These hyperfine
splittings broaden the line by approximately 2.5 MHz.
Since llteSe light molecules are easily excited in high temperature and density
regions, the search of metal hydrides may best be done by observing high J lines
with high-Frequency observatories such as Herschel and SOFIA. or by absorption
spectroscopy in the J = I —> 0 line toward infrared continuum sources.
In addition to diatomic molecules. molecular crystals containing a large number
of metals may also exist in space. It is possible that these molecular cystals can be
detected by their vibrational spectrum in the infrared (Section 13.l).

7.13 Raman Scattering

Emission and absorption of radiation are nor the only processrs that can be used to
study molecules. Incident radiation can cause an induced dipole moment in a moleflllf-
as a result of the electrons and nuclei moving in opposite directions in response to the
electric field. As in the atomic case (Section 5.7), oscillation of this dipole moment can
lead to Rayleigh scattering. However. if this oscillation is modulated by the internal
motions (vibrational. rotational. or electronic) of the molecule. a shift of frequency
can occur and this is known as Raman scattering. Since Raman scattering can occur
in response to visible light. one can obtain information of electronic. vibrational. 01'
rotational transitions on molecules without using ultraviolet. infrared. or millimeter
spectroscopy.
 7. I3 Ramon Scattering 253

Table 7.1]
Examples of rotational transitions of hydrides

Molecule Lowest transition A (run) 1: (GHz)

Nan J = 1—4 0 1034.1 209.9

artho—H30+ J. = 21 —> 11 975.9 307.2
Mg“ 22+; =1/2. N = 1.» 0 074.0 343.0
ortho-HZD+ 35K“ = I”, —~ 1II 005.0 372.4
Lil-I J = 1 —» 0 675.2 444.0
HIS JKpKo = i” -" Om 662.7 452.4
cu 2nmr = 3/2 —.1nmJ = 1/2 562.0 532.7
NH. 1K = 10 -+ 00 523.7 572.5
HC} J = 1—> 0 479.0 625.9
511-1 2l1,.,-1J’=31/'2-rl/2 454.2 660.1
c1-1+ J = 1 —> 0 359.0 035.1
NH 1: N = 1—> 0 307.6 974.6
para-1130+ 3,. = 1., -> 00 304.5 904.6
H20 1'8“»: 1..—'00: 269.3 1113.3
pom-H2D+ 3th = lo. -> 000 210.2 1374.0
SH 2mm; = 5/2 _. 3/2 216.0 1302.0
HeH+ J = 1—» 0 149.1 2010.7
CH2 3K7.“ = 1.. —> 0mJ 127.9 2344.0
011 2nmJ = 5/2 —> 3/2 119.4 2510.9
HD J —. 1-» 0 112.1 2674.4
1-12 .1 = 2 —> 0 20.09 10672.0

Adapted from Blake. GA. I985. PhD. thesis. Caltech.

The selection rules for Raman rotational transition in linear molecules are A J’ = 0
(Rayleigh scattering) or 3:2 (S branch). For vibrational—rotational transitions. die
selection rules for diatomic molecules are Au = :|:1. 111.! = O (Q branch), i=2 (0 and
S branChes).
The vibrational transitions in highly symmetric structures such as diamond are
largely forbidden. Crystalline graphite is also almost featureless (with the exception
of a feature at 11.5 urn). making it very difficult to identify in the ISM. However.
crystalline diamond and graphite have Raman peaks at 7.5 and_6.7 urn. respectively
(Fig. 7.38). With future advances in astronomical infrared spectroscopy, it may be-
come possible to probe the vibrational modes of these substances by Raman spec-
troscopy.
254 Interstellar Molecules

230 . 1— . . . ,

260

Intensity (a.u.) 240

220

200

180

"50
[300 [400 I500
Raman shift (em l)

Figure 7.33
Laboratory Raman spectrum of a diamond thin film prepared using hot filament chemical
vapor deposition. The sharp peak at l332 cm" (7.5l pm) is due lo diamond. and Ihe broad
feature at ~ 1500 cm '1 (6.67 lum) is due to graphite (from Chen er al. 2002. J'. Chem. Phys.
116. I21 I).

7.14 Summary
Advances in millimeter—wave and infrared spectroscopic observations since the [9705
have clearly demonstrated the richness of the gas-phase chemistry of the ISM. Among
the over 120 interstellar molecules identified. the whole family oforganic chemistry is
represented. This includes hydrocarbons. alcohols. acids, aldehydcs. ketones. amides.
esters. ethers. organo-sulfur, acetylene derivatives, and so fonh (Table A3.2). In W5
of abundance, formaldehyde (RICO) and hydrogen cyanide (HCN) are the MOS!
abundant polyatomic organic molecules observed. Ammonia and fonnaldChydc are
interesting prebiotic molecules since they can be chemically combined to produce
amino acids. Hydrogen cyanide (HCN) can turn into HCN polymers, which in turn
 Exercises 255

can react with water to form heteropoly'peptides. precursors of proteins and nucleic
acids.
Among the four major classes of biomolecules—proteins. nucleic acids, lipids.
and carbohydrates—shople forms of carbohydrateS (sugar) have been detected.
Amino acids are the building blocks of protein. and there is strong evidence that
the simplest amino acid (glycine) has also been detected. Technical advances in re-
ceiver technology and telescope designs have increased the level of sensitivity to the
extent that the detection of new molecular transitions in the m and submm regions
is no longer limited by sensitivity but by line confusion. As we begin to search for
more and more complex moleculfi, the increase in the number of transitions rapidly
fills up the spectral window. It is therefore not clear how much further one can push
in the use of mmlsubntm rotational spectroscopy to search for biomolecules, even if
they are present and common in the ISM. A more promising approach may be the use
of vibrational spectroscopy in the infrared, as this discipline develops further through
the use of air- and space-home telescopes (Chapters 8 and l I).
It should also be noted that as of the beginning of the tWenty-lirst century.
hundreds of astronomical lines in the millimeter and submillimeter regions remain
unidentified. Part of the problem is the lack of laboratory or theoretical estimates
of transitions of unstable molecules or molecular ions. Close collaboration between
astronomical and laboratory spectroscopy is therefore important in the future growth
of the discipline.

Further Reading

Herzberg. G. 1950. Spectra oth'atomr'c Molecules, Van Nostrand Reinhold.

Hollas. J. M. I998. High Resolution Spectroscopy, 2nd ed., 1. Mley & Sons, New York.
Townes. C. H. and Schawlow. A. L. I975. Microwave Spectroscopy. Dover.

Resource Materials

Molecular line lists:

Jet Propulsion Laboratory Molecular Spectroscopy Database:
http:spec.jpl.nasa.govlhorne.html
Cologne Database for Molecular Spectroscopy:
hnpzllwww.phl .uni-koelin.delvorhersagen/

Exercises

l. he lowest rotational transition (J = 1 — 0) of 12clto has a frequency of 1 15.271202

MHz. Using eqs. 7.4 and 7.2. calculate the frequencies of the same transition in 13C '60
and ”die.
2. Calculate the statistical weights of the J’ = O. l. 2. . . .7 rotational states of H2.
256 Interstellar Molecule:

3. Write down the possible hyperfine transitions of the J' = 1—» 0 and J = 2 __’ l
rotational transitions of CV70.
4. N0 has an unpaired electron and therefore nonzero electron spin quantum number
(S = I2‘2). The interaction between the electron spin and the rotational angular mo-
menta can lead to A doubling. Fmfl'lermore. N has a nuclear spin of I = I. lfthe
ground electronic state is X2111”. what are the possible hyperfine transitions for an
rotational msition J = 11/2 —> 9/2?
,._8
Vibrational Spectroscopy
of Polyatomic Molecules

In general. 3N coordinates are needed to specify the locations of each atom in a

molecule with N atoms. As a molecule undergoes translational motion, 3 coordinates
are needed to specify the center of mass of the molecule. When the molecule rotates in
space, 3 more coordinates (angles) are needed to specify the orientations of anonlinear
molecule. Since these 6 coordinates refer to the motiou of the molecule as a whole,
the displacements of the atoms relative to each other (while the molecule maintains
a fixed position and orientation in space) can be determined by 3N —- 6 coordinates.
Consequently. a nonlinear molecule has 3N - 6 modes of vibration associated with
these internal coordinates. For a linear molecule. only two angles are needed to specify
its orientation, therefore 3N — 5 modes of vibration are present.
These modes can be separated into stretching (when the lengths of the bonds
between two atoms change) and bending (when the bond angle between three atoms
changes). Often vibrational modes are classified as symmetric or antisymmetric. For
example. in a triatomic molecule like C02, the symmetric stretch refers to the case
where the C—0 bonds shorten and lengthen together in unison. An antisymmetric
stretch refers to the case when one bond shortens (0 moving toward C) while another
bond lengthens (the other 0 atom moving away from C). A third mode for C0;
is the bending mode, when both 0 atoms move in the same direction off the 0-—
C—0 axis. There are two ways that 0C0 can bend—in the plane of the paper and
perpendicular to it. These two modes of vibration, however. have the same frequency
of vibration and are said to be degenerate (see example of HCN in Section 8.1).
These 3 x 3 — 5 = 4 metions constitute the normal modes for CO; and generate three
vibrational frequencies.
When the displacements along the normal coordinates result in changes in the
elecu-ic—dipole moment. electric-dipole transitions are possible and this mode is re-
ferred to as infrared active. For example. the symmetric surtching modes of a 3-atom
linear molecule XYX and a 4-atom linear molecule XYYX leave the electric-dipole
moment unchanged. and therefore are infrared inactive modes. The infrared active
and inactive frequencies of a 4-atom planar molecule (YXJ) are shown schematically
in Figure 8. I. Since there are degeneracies. the number of frequencies is smaller than
the number of modes.

25?
253 “irrational Spectroscopy ofPolyaromfl: Molecules

O 0
V: V2 V4
Infrared: Inactive Active Active Active

Figure 8.1
The vibrational modes of a planar molecule YXg. The arrows indicate the direction of motion. and
"4-" and “—“ indicate motions in and out of the plane of paper.

3.1 Linear Molecules

A linear molecule with N atoms has N — l bonds and therefore N -- 1 stretching

frequencies. This leaves [3N — 5 — (N — 1)] = 2N — 4 bending modes Since the
bending modes for linear molecules are always doubly degenerate with two modes
associated with one frequency. there are N — 2 bending frequencies. In order to
visualize this double degeneracy. we can consider a linear molecule like HCN. where
the molecular axis is considered as the z axis. In this case. the bending of the H and
N atoms relative to the C atom in the .r and y axes is equivalent, and therefore the
bending modes are degenerate (Fig. 8.2).
When we add the N — 2 bending frequencies together with N - 1 stretching
frequencies. we have a total of 2N — 3 fundamental modes. These modes are denoted

d—O—Q—O—O-ub VI CN WI! 2039

i I v, Bend 7l2

®--O-—-®
‘—O——O"—'O"’ V3 CHstretch 33l2

Figure 3.2
Illustrations of the stretching and bending modes of HCN. The “+" and “—" signs signify
motions in and out of the plane of paper (adapted from J.M. Hollas [998. High 395011150"
Spectroscopy. p. 107).
 SJ linear Molecules 259

as ul, v2. U3. . . . and so on. The quantum states of a polyatomic linear molecule can
therefore be written as ulvzv3 . . . um 3. For example. HCN has 2(3) — 3 = 3 modes:
”I corresponds to CN stretch. u; corresponds to the two degenerate bending modes.
and v3 corresponds to CH stretch (Fig. 8.2). An example of a vibrational energy level is
01 l. standing for u] = O. u: = 1. v3 = l. The fundamental modes of HCN are therefore
pl (100 —> 000) at 4.8 um. 02(010 —r we) at l4.u.m. and v3(00l —> 000) at 3pm.
Some of the lower transitions of the v2 bending mode are shown in Figure 8.3.
For C2H2. 2(4) - 3 = 5 and 5 quantum numbers are needed (e.g.. 01 IOO). The
1)., and v5 bending modes are doubly degenerate with two modes associated with each
frequency. For a degenerate bending mode u... (HCN. mode 1);). which corresponds
to the two-dimensional harmonic oscillator. the energy level n has a degeneracy
of u + l.The quantum number associated with vibrational angular momentum is
denoted as l. The possible values of '1] are n, u — 2. . . . . O or 1. A single positive
value of [II is used although :l:.l| are possible. The double degeneracy for each
value of l is associated with clockwise or counterclockwise motion of the nuclei
in a linear molecule. Sometimes Greek letters are used to designate vibrational
angular momentum (in analogy to the use of E. 11 . A. and so forth. to represent A =
0. l, 2. . . . for lltecomponent oforbital angularmomenlum abouttheintemuclearaxis
of a diatomic molecule) and l is often written as a superscript. such as r13. [1‘ the two-
dimensional oscillator is anhannonic. the difierent .ll values are split by a few cm 1.
For molecules with a center of symmetry. 3 and u are used to indicate the symmetry.
Some examples of the bending energy levels of a linear u-iatomic molecule are
000. 010. 020. and 030. For 000 and 0I0. the only possible values for l are 0 and 1,
respectively. For the level 020. I can be u; — 0 = 2, or v: - 2 = 0. and the levels are
designated as 0220 and 0200. For the level 030. I can be u; — 0 = 3 or U; — 2 = 1
and the levels are designated as 0330 and 03 '0. Consequently, the energy diagram can
be quite complicated even for a linear triatomic molecule. As an illustration of these
notations. part of the energy diagram of C02 is shown in Figure 8.4. Some of the
transitions are detected by ISO (Fig. 8.5).
The double degeneracy of the v2 bending mode is lifted when the molecule is
bending and rotating simultaneously. This is known as l-type doubling. Since the
splittings are small, the Hype transitions occur at low frequencies and can be observed
by cm-wave telescopes. For example, the frequencies of the Hype transitions of the
first excited bending mode of HCN is approximately given by v = (H (J + l). where
q z 224 MHz. Some of the observed l-type transitions are listed in Table 8.1.
In addition to A1 = 0 transitions. rotational transitions with A} = :l:l can also
occur (Fig. 8.6). Figure 8.3 shows that the GNU and 0220 v2 states are split into
two levels each. Rotational transitions (J = l —> 0. 2 —-> I. 3 —> 2 from the (OIO) and
(020) vibrational states of HCN were first detected in Orion and IRC+10216. Most
interestingly. some of these lines are found to be strong masers in lRC+10216.
In addition to the vibrational transitions (fundamental. overtone. hot bands)
discussed in Section 7.5. transitions involving changes in two or more modes are
possible. These transitions. for example. OH H» 000. are called combination bands.
Two examples of combination bands in C0: are shown in Figure 3.4.
260 Vibrational Spectroscopy afPalyamnu'c Molecules

fi‘fi

.2°.o —— (Mk-0)
200° L (o ) (0.2110; 4

8
kl

: 7.2m (0.1".0) ‘
'000 “ A=2.15" (0.1“.0) J

0 r (0.0.0) ‘

Figure 8.3
Energy levels (an-anged in columns of constant I) of the lower bending modes of HCN WWI
transition frequency and spontaneous emission rates listed (adapted from Ziurys and Turner
1986. ApJ. 300. L19).
 a 1 Linear Molecules 261

3000 __ “I0
——03'0

15.40.11"! I343 ym

2000 -- NW
0220
0200

E __
t- l3.B'H-lm l6.l3pm

l000 ‘—
OI'O

“T 14.97pm

0 —— ——OD“0

Flgure3.4
The energy levels ofCO; showing some ofthe transitions in the mid infrared. 'll'te 0| l0 -> 0000
is the fundamental v2 bending mode. The 030 -—D 00.0 and 0'20 —> 0I0 are examples of hot
bands. whereas the transitions between adjacent columns (")0 --> 010 and 110 —> 020) are
combination bands (adapted from Heals-erg I966. Infrared and Roman Spectra ofPolyatomic
Molecules, Van Nostrand Company. New York).

Acetylene (H—CzC—H) is a symmetric linear molecule with four atoms.

Therefore it has 3(4) - 5 = 7 vibrational modes. of which 4 — l = 3 are stretching
modes and 7 — 3 = 4 are bending modes. The transition frequencies of these modes
are summarized in Table 3.2. Each vibrational transition is actually a band made up
of many rotational lines Iliat are grouped into P. R. and possibly. Q branches. Strong
features are expected to be observed in the Ill-um region due to the active ”5 fun-
damental band with a strong Q branch centered at 13.7 pm (729 cm“). Several “hot
bands" with strong Q branches are also located in this region (Fig. 8.7).
262 Wbral'ianal Speclroscopy ofPolyaromic Molecules

Flux (1y)

§
L-l

t_I_.lIILrILlJJ_IJJ_ii
12 l3 i4 l5 l6
Wavelengh gum}

Figure 8.5
ISO SWS specua of two oxygen-rich AGB stars showing the vibrational transitions of C01.
The five transitions in Figure 8.4 are seen in emission in EP Aqr. No transitions. 1090 -b 01'0
and 01'!) —> 00°O (fundamental v1). are seen in emission and absorption. respectively, in W
Hya (adapted from Justtanont et at. 1993. AM. 330, LI'IJ.

Table 3.1
l-type mitions in the u; = l
vibrational state of HCN

1 Frequency (MHz)

4.48343
I6. I 48.55
20. I8] .40
IO 24,660.31

1l 29,554.66
l2 34.95176
13 40,766.90
I4 47,023.20

Observed frequencies in AFGL BIB

(Thomirlh e: ai. 2(1)]. ApJ. 536. 338).
 1301.5
. HCN. 111:1 I i Z
1425 _- j . -
; 13——r : g ;
1400 _— —_ I I
C I - ’:——f 31307.0
1- - " I '

1315 _— -_ I / I
. . . I -
- - I, 4

_ 12 - - 1’ .
1350 — - ,4. -
I I" i 2
j 1’: ~ — 1300.5
3 1325 _- ’1 j .
5 - / : 29,584.66 MHz :
. 11 i - , I
1300 _- \ j .
\—
\\ - '
.
. \. . ..
1215 - 1—
\ -
—\ \-
—1306.0
-

:
. 10
' \K: \
I
3:
1250 - - . ‘1 .
> - _ \ -
1. . \
'- _ 1- \— a 4

1225 L _‘ _— — 1305.5
2 9 I -
. J L .
1200
Figureflfi
The rotational levels of the ground-state bending mode (112 = I) of HCN. showing the possible
unmitions with A] = :|:l and A] = 0 (from Thorwirth er al. 2003. ApJ. 586. 338).

Table 8.2
Vibrational modes of acetylene

Mode 11 (cm-‘) J. (um)

Symmetric C—H stretch v. 3373 2.96

C=C stretch v; 1974 5.07
Antiaymnwu-ie C—H stretch 113 3295 3.03
tram bend J.H—CEA(3—HT u. 612 16.3
at: bend lH—cEc—Hl us 129 13.7
AW! indicate bending directions. For definition ol'mms end et's. see
Section 9.1]. Tible ndapted fmtn Bennth. I'. F. I995. Spectra ofAtanu and
Molecules, Oxford. p. 245.
264 Vibrational Spectroscopy of Polyaromh: Molecules

. , . . .
HCN 252'" 5' HCN 2&0 _ l5t
HCN 3 'i3 2 'i2 "C“ 'i' l "
[ — HCN Elmal + 25°

2.510‘ -

lll'lllllllllllllllll
F (J!)

C2H22‘QOH'EI—2'io
'l :l' 1 I l l l l l l l l l l

C: :2 v,“-13% anvil—W“? & W415."

i C: V." + 's' - V.‘
2.010‘ - c2142 2»: + v,“ — 2a” L'Czl‘lz 2%” + vs' 4"} & 3v; - 2"}
& 2&2 + 131—211" C214: '3' + 215‘ - ”4' + It" ‘
C1": ‘1' ‘l' 2'’50" ’3." + "a
l I I
CIH”
1 2”5 —|""
tint-295+»;
——l HC'JCH v; & c2112 I5'+t3‘l—I5'
—v I <
l n
’ C2": ”5' & hi- '3'
1 l a l . I 1 . | .
13 14 15
3- (Hm)
Figure 8.7
ISO spectrum of lRC+102l6 showing the v5 fundamental bending mode of C2H2 at I33 um and its
associated hot and combination bands (from Cemicharo er al. I999. ApJ'. 526, L41).

8.2 Symmetric Tops

3.2.1 H;
The simplest polyatomic molecule is the H; molecular ion (Secu'on 7.] l). with three
protons held together by two electrons in an equilateral triangle. It has 3(3) — 6 = 3
modes of vibration, with u. (at 3 I76 cm", or ~3 um) corresponding to simultaneous
stretching of all three sides of the triangle and all three protons moving away from
the center of mass. The other two degenerate modes v; (at 2512 cm'l. or ~ 4 um)
correspond to the stretching of one (or two) side of the triangle while the other two (or
one) sides are comraeting. The double degeneracy of 1:2 is broken when the molecule
is rotating (Section 8.1). Since the electric-dipole moment is unchanged in u]. it is
infrared inactive.
The U1 = l (- 0 vibrtational transition overlaps with part of the L-band anno-
spheric window. and can be observed in absorption against strong infrared continuum
sources. Some of the strong absorption lines in the 3-4 pm region that can be observfll
astronomically are shown in Figure 8.8. The quantum number G = llt * lzl is "99"
 8. 2 Symmetric Tops 265

instead of K for l; 7': D (for the first excited state shown in this diagram, l: = :l: l). The
labels a (for upper) and l (for lower) on the rotational levels of the excited v2 state
refer to the different combinations of k and (2 with the same G. For electric-dipole
transitions. the selection rules are A1 = 0. :l:l and K = G. The latter rule resuicts
these vibrational-rotational transitions to within the same column in Figure 8.3. For
example. the transitions RU = 1. K = O) and QU :1, K = D) are at 3.6635 and
3.9530 urn. respeCtively.
Since H; has three protons. it can be in the orrho (I = 3,!2) or para“ = 1/2) form
and does not convert from one to the other easily. Since the rotation of the molecule
by [20" is equivalent to the exchange of two pairs of protons. the molecule is in artho
form if K is a multiple of 3. as in the case of ammonia. The (O. 0) state, as well as all
even J states of the K = 0 column in the ground vibrational state. are forbidden by
the Pauli exclusion principle. The lowest allowed rotational states are (J = l, K = O)
and (J = t, K = l) for ortho and para states. respectively. In the low-temperature
environment of molecular clouds, the H; ion resides primarily in one of these two
states. The relative population of these two states is governed by proton exchange
reactions (Section 14.5.4).
H; is a nonpolar molecule without a permanent electric-dipole moment and
therefore has no permitted rotational transitions. However. centrifugal distortion can
produce a small dipole moment in the plane of the molecule. The selection rules
governing these forbidden rotational transitions are AJ 2 0. :H and AI: = :l:3. and
some examples of these rotational transitions in the ground vibrational state are shovm
in Figure 8.8. The strongest rotational transition is expected to be (J = 2, K = 2) ->
(J = I, K = l) at a wavelength of95 um and A ofB x to 7 sec". in this diagram.
the K = 2 4-) 1 transition in fact corresponds to k — 1.2 (a 21:], so the selection rule
is indeed satisfied. While most of the low-lying rotational states can decay to a
lower level ((2. l), (2. 2). (3, 0). (3, l), and (3. 2) have lifetimes of 20.4 d, 27.2 d.
3.8 hr. 7.9 hr. and [5.8 hr. respectively). the (3. 3) state has nowhere to go and is
therefore metastable. This results in the overpopulation of (3. 3) and the possibility
of observation of the R(3, 3) vibrational-rotational transition.

8.2.2 Hydrocarbon Radicals

Another symmetric top similar to H3+ is the methyl radical CH3. Due to its symmetric
planar structure. CH3 does not have an elecuic-dipole moment and therefore has
no permitted rotational transitions. For the same reason as Hg, its v, symmetric
stretching mode is infrared inactive. The strongest vibrational mode is the u; out-
of-plane bending mode. As in 1-1;. the K = 3. 6. 9, . . . states are associated with the
ortho (I = 3/2) form. with the other K states associated with the para (1 =.- ”2)
form. The Q branch of U: at 16.5 am was detected by ISO in Sgt A'. [n the diffuse
ISM. the methyl radical is believed to be formed by proton transfer (eq. 14.33) or
radiative association (eq. 14.4) followed by hydrogen abstraction and dissociative
recombination (eq. 14.50) reactions.
Hydrocarbon radicals are believed to play an important role in the photochemistry
of the atmospheres of giant planets. Ethane (Czflé). for example. is formed by the re-
action of two methyl (CH3) radicals. Radicals such as CH. CH1. and CH3 in planetary
atmospheres are the result of photodissociation of methane (CH4). the most abundant
 G=0 I 2 3 4 5
I r l l l i
3500— H 2
- I R _

_ " 4
[Int 1-..! jsoo
I
_.. I—___ -
_ _ u fi
3000- J=3 4L 1; .
—-—-L —4ooo
_ J=2 u :
L g —
_ 1:]
3
2500-J=0 I ‘5 —_(soo
' a a j
_ - «i
L 3‘ r. 52' '
c-i a .1; —3000
_ K, N‘ m" -
F a 51 5 -
2000 .. :5? a ..
_ gtfif d -

=— _ all ABE a: —2500_.

E
.3 _ r6!
'. '17.:
:N
-.=:
n
-_ M
I:
3 Gang t'i
~ 8_ a: an: a: '
1500 E :u 5 —2mo
b A “E- II: 4

_
°.
M
912:;
—I"' "1 -

'_
aas=
a a“ u
--
E: :- —I5{D
moor °‘_ '

Figure 8.3
The rotational energy levels (shown in shaded areas) in the ground and in the v2 vibration-l
excited state of H}. The orrho (l, 0) and para (1, I) are shown as thick horizontal bars.
The metastable states (3, 3) and (5. S) are shown as ticked horizontal bars. The + and - signs
above each rotational state are the parity (=(— D" ). The vertical lines (K = G) are vibrational-
rotational transitions of the fundamental uz bending mode. whereas the intercolurnn lines 816
very weak pure rotational transitions (from Goto er al. 2002. PAS]. 54. 951).
 3.2 Symmetric Tops 26'!

5 I I I l I l l I l l _l_ I I I I d

: Q0. 1) 90.2) a
_ 9(3. 3) Q(4, 4) j

A 3 '— Qto. 6)
Il -—
_‘
5‘ 2 9(5, 5) 2
I _ —
E 2 .. Qfifl) I (20. I) 96.2) _

1L .2
: 3
0 ' I I l I I I J l I I I L l I 4
16.45 16.5 16.55
Wavelength (pm)

Figure 8.9
[50 SWS spectrum of Neptune showing the v2 band of CH; (adapted from Bezard er al. 1999.
ApJ. 515. 363).

hydrocarbon in these atmspheres. While methane. ethane, and acetylene have been
observed in planetary atmospheres from ground-based and Voyager observations. the
hydrocarbon radicals Were first detected by ISO. Figure 3.9 shows the detection of
the methyl radical in Neptune, including the 20‘! = l, K = l). Q(2. 2). 9(3, 3).and
Q(4, 4) transitions of the I); hand at 16.497 urn. as well as the QC], 7) at 16.458 um.
Q06. 6) at 16.474 um. Q(S. 5) at 16.436 ,um. :20. I) at 16.531 um. and Q0. 2) at
16.551 ,um.
As another example for the discussion of the vibrational spectrum of a symmetric
top molecule, let us consider CHJF. This S-atom molecule has 3(5) - 6 = 9 modes
of vibration, with four stretching modes corresponding to the four bonds (3 C—H
stretches and one C—F stretch). The remaining 9 - 4 = 5 are bending modes. One
example of the bending mode is when all three of the F—C—H bond angles change
in the same direction. This motion is similar to the opening of an umbrella and is often
referred to as the umbrella mode.
Figure 3.10 shows the normal vibration mode of HZCO. When two of the H atoms
bend in the same direction against the C atom like a rocking chair. it is referred to as
a rocking made. Vrbration as the result of a twisting motion between two rigid pans
of a molecule is known as a torsional mode (Fig. 8.11). When two H atoms attached
to a C atom (e.g., as in a methylene group) bend out of plane in the same direction.
it is known as the wagging made. These bending modes are sometimes referred to as
deformations.
26B Wbrarional Spectroscopy of Polyatomic Molecules

/
*— -+

1199 cm" [752 cm"

Out-of-planc bend C—O stretch

\ /

l /'
1273 cm I 2933 cm" \
CH2 rock C—H stretch

\\ /

’4'

1549 cm" 306] cm"

CH2 bend Antisymmeuic
C—-H stretch

Figure 8.10
Illustrations of the stretching and bending modes of formaldehyde. The “+" an “—" signs
signify motions in and out of lhc plane of paper (from Bissonnelte. C. 2003. Handbook of
Molecular Physics and Quantum Chemistry. Ch. [2. Wiley).

H 0

\C //
0
// {3—3 H

Figure 8.11
Illusuation of the torsional vibralion about the C—C axis in rrans—gloyoxal.

3.3 Asymmetric Taps

The water molecule is an asymmetric lop (Section 7.9.2) with 3(3) — 6 = 3vibrali0nal
modes. The two stretching modes are vl symmetric stretch C—H at 3651m']
(= 2.74 turn) and v3 antisymmetric C——H stretch at 3756 cm" (= 2.66 uml- The
v2 bending mode (1595 cm". or 6.3 pm) corresponds to the two H atoms moving in
the same directiou as the H—O—H bond angle changes (Fig. 8.12). The vibrational-
rotational transitions of H20 are detected by ISO. Figure 3.13 shows the ISO SW3
 3.3 Asymmetric Top: 269

0
v. 3651 cm" /*\
Symmetric snatch H H

\/‘+’\/
v2 1595 cm" bend H

0-b-

v, 3756ch H/ \H
Anusymmem'c snatch /
Figure 8.12
The normal vibrational modes of H20 (adapted from Bernalh. P. F. l9'95. Spectra ofAronu
and Molecules, Oxford. p. 270).

350
Flux (Jy)

7.50

5.5 I I I 6 I 6.5 1
3mm)
Figure 3.13
The ISO SW5 spectrum of Orion BN/KL showing a forest of (unmarked) emiasion and
absorption lines due to the u; = l —-> 0 bending mode of H20 (from Gonzfilcz-Alfonso er al.
l998, ApJ. 502. L169).
270 Vibrational Spectroscopy ofPolyatamic Molecaler

—'-‘———t—

In; (2—0 stretch

3 x 6 — 6 = 12 figs

v3. ”9-”:
pr V1 1 CH3 rocks C—H stretches
1’6 OH bend
v5, um. 13 CH3 defonnations V. 0—H match
.I j I l I r I l l I t l l I I _L _l t .

500 1000 1500 2000 2500 3000 3500 4cm

Figure 8.14
The 11 small-amplitude vibrational modes of methanol lie in the infrared between 3 and
10 pm. The all torsional mode is not shown (from L. H. Xu).

spectrum of Orion BNIKL at the 6.3—).tm band, where the R branch (A. < 6.3 Jrim)
transitions are seen in absorption while the P branch (1 > 6.3 pm) transitions are
seen in emission. The high abundance of water vapor in the Earth‘s atmosphere and
the strength of its vibrational and rotational (Section 7.9.2) bands are responsible for
the strong absorption of the outgoing thermal emission from Earth. ‘ntis results in a
20—30 K increase in the Earth's average temperature. making water the most important
greenhouse gas.
In addition to absorbing the Earth's radiation. water vapor in the atmosphere also
absorbs incoming sunlight. Since the stretching modes (v1 and 03) are approximately
twice the bending mode (112) frequency. water has overtone bands at approximately
3. 4. 5. and so on, times the 1;: frequency. Since the over-tone bands extend to visible
wavelengths. they absorb ~ 10—20% of the solar radiation, and therefore warm the
atmosphere.
Methanol (CH3OH. Section 7.9.3) has six atoms and therefore 3(6) - 6 = 12
vibrational modes. They correspond to 0—H stretch (v1). C—l-I stretches (v2, v3. vg).
C—O SUCIClI (Us), CH3 rocks (”1, I" I)' OH bend (U6), CH3 deformations (”4. ”5. ulo).
and um torsion. Figure 8.14 shows the frequency ranges of these vibrational modes.
The C—H stretches are observed in emission in the 3-um spectra of Comet bee
(Ctr 1999 H1) by the NIRSPEC instrument of the Keck Telescope.

8.4 Carbon Chains

New carbon chains can be produced in the laboratory from unsaturated molecules
such as acetylene (Czl-Iz) and diacetylene (CA-[2). Examples include cyanolitollilms
 8.4 Carbon Chains 2'11

(HCHN). isocyanopolyynes (HCZHNC). methylpolyynes (H3C2.,+.H). methylcyano—

polyynes (H3CZRN). cumulene carbenes (Hzcn), ring-chain carbenes (C2,l+ 1H2.
HEN), and free radicals (CnN). These asymmetrical carbon chains are highly po-
lar molecules and their large dipole moments allow their rotational transitions to be
detected by millimeter-wave spectroscopy. In fact. the simpler carbon chains (e.g..
CCH. CCCH. . . . Call) were discovered in the ISM before they were synthesized in
the laboratory. The largest urban chain detected is HC. .N. It has a molecular weight
of 147. twice that of the simplest amino acid glycine (NHz—CHZ—COOl-I. molec-
ular weight 75). As the length of the chain increases. the abundance ratios between
consecutive cyanopolyyne chains HCanNIHC2n+3N are ~ 3 — 5 for n = I - 4. The
abundance of the HCan family is much lower, with an abundance ratio l-lCCNl'l-IC3N
of ~ 200.
If we approximate carbon chains by a uniform thin elastic rod. we can calculate
the classical Young's modulus from the ratio of the centrifugal distortion and rota-
tional constant. It is found that the stiffness of carbon chains can be higher than that
of steel and diamond.
In addition to acetylene. which is commonly seen in carbon-rich AGB stars. poly-
acetylenic chains are detected in protoplanetary nebulae. The fundamental bending
modes as of diacetylene (C41-l2) and v” of triacetylene (Cal-12) at 15.9 and 16.1 pm.
respectively. have been detected by ISO in AFGL 6|8 (Fig. 8.15). Also seen in this
specu'urn are the bending modes ofcyanopolyynes, including v2 of HCN, us of HC3N.
and u; of HCsN.
Examples of carbon chain radicals include the carbon chains (CRH) with one
nonbonding electron and cumulene carbenes (cg, H2C3 and H3C4) with two non-
bonding electrons. These molecules have very strong rotational u-ansitions because
of their linear or near-linear geomeu-y. and their high dipole moments due to the non-
bonding electrons. Figure 8.16 shOws the increase of the dipole moment of carbon
chains with increasing chain length.
The unpaired electron of CnH leads to a 211 electronic ground State'. As in the
case of OH (Section 7.10.1). coupling of the spin angular momentum of the electron
to the orbital angular momentum and the molecular rotational angular momentum
Splits the 1ill state into two fine-structure components 2'1] m and 2[11.2. and each in
turn is split into two components by A doubling (Section 7.10.1). For C2,,H. 2113.12
has lower energy. whereas 2“ “2 is lower in energy for CZn-HH'
We should remember that the fact that these carbon chain radicals are easily
detected in the ISM does not imply that their fonuation is favored by the interstellar
chemical network. but rather reflects theirlarge dipole moments and their linear geom-
etry. which results in smaller partition functions (Section 9.1). Nonlinear molecules
of similar or even higher complexities probably also exist. but their rotational tran-
sitions are too weak to be detected because the molecules are spread over too many
rotational states (Section 9.3). This phenomenon is known as line dilution.

1. For C1,,H. CzH and C..H have 22; ground states. but switch to 2H for the longer chains.
 2000! ' __________

lfith‘m erg cm‘ 1 s ')

500 ,_ A i 1 _ l . I J
13 I4 15 [6 n
Wavelength (pm)

Figure 3.15
ISO specu-um of AFGL 613 showing the vibrational—rotational transitions of polyyncs (C‘Hz‘
C6H1). benzene. and cyanopolyyncs.

l I I l l 1- -—|

Cumulcnes
10 L "IC. _
1
B - 1
1 / Acctylem'c radicals HC_ .

e 6 - n __ - a -
a. , .o-
, Cyanopolyynes HCIN

4 - s, -
-
a la"
.ea‘
2 r- ..

L l n l A l . I l 1 I 1 I

2 6 IO 14

Figum 3.16
The increase of the dipole moment of carbon chains as a function of the number of carbon
atoms n in Ill: chain (from McCanhy e: all. 1997. ApJS. 113. 105).
 8.4 Carbon Chains 273

°,0)
c i v,(0.l'.0)t-(D.0
Band center

003) I2)
0(4) a Qué’ 3(6) R(B) "(10) RGZ)

PIE) H6) 0(20)

Km) ”4’ 004)

i
__'_‘ I . .
T)
. . ,
i .fi ,fi f. . 1 fl
| 0””
. fl 1—.
I700 1800 1900 2000 2100 2200
6H: OH: OH: OH: 6H: GHz

001) l,955.648.96(8) MHz R(2) 1.968.595.4(1) MHz

Figure 3.17
Comparison between the theoretical spectrum (top) ofthe I»; (band center 157.69 urn) bending mode
of C; with the lubomtory measured spectra of the Q(12] and R(2) transitions (bottom) (adapted from
Git-sen eta!.200l.ApJ.551. L181).

Since the proposal by A. E. Douglas in 1977 that pure carbon chains (Cu)
could be responsible for the diffuse interstellar bands (Section 12.3). there has been
increasing interest in these molecules. Electronic transitions of C2 and C; have been
detected in the photospheres of evolved stars (Section 7.2), and the vibrational—
mtational u-ansitions between different electronic states of C3 have been observed
in absorption against background hot stars (Fig. 7.6). "file C,l carbon chains have no
permanent electric-dipole moment and cannot be detected by radio telescopes through
their rotational transitions. However. they have asymmetric stretching modes around
~ 5 um and bending modes around ~ “30 pm, which can be detected by infrared
spectroscopy. For example, the antisymmetric stretching modes of C3 (:13 at 4.90
um or 2040 cm I) and C5 (05 at 4.62 pm or 2164 cm'l) have been detected in
absorption in warm environments such as the circumstellar envelopes of carbon stars.
Triatomic carbon (C3) has a vibrational bending mode 02 (0, 1‘. 0) <— (0. 0°. 0)
near 153 um (Fig. B.l7), and this transition has been detected by KAO and ISO in
absorption against the dust continuum of Sgt B2 (Fig. 3.18). For the higher members
Z74 Wbmimal Spectroxcopy of Polymamir Molecules

: I T I I l l 'l I I I I 1—:

1.00 .—- me
E :
0.95 r g
5 = 5- 0(2) 5
0.90 - . 1 1 l 1 .-
fl I T I If I r I I I I . .
LN _ . , ‘1

E I
OBSE- —:

0.90 — 3
'5 :
LCD Eh- _

0-95 r1: 143.330 um m6) ‘-

I I I 41 l AL I n_ I l 41 -
fir l r l 1 I I I I I 1}
will-Ill!
Line fludconlinuum flu:

LII)

0.90
A = 167.679 pm

1.“)

0'90 J. = 158.059 pm
I I I J I L I l
I' I

EA=IS4.862 pm 900)
0.95 l _L _L r_ J— 1 1—1 I a 4|
—200 400 0 IN 200 300
um (km s")

Figure 8.18
150 LWS Fabry—Perot speclrum ongr 32 showing several bands of”: L5 banding mud: 0‘
C3 near 153 um (adaptnd from Cemicham el‘ at. 2&0. ApJ. 534. L199).
 8.5 Polycyclic Aromatic Hydrocarbons 275

of the pure carb0n chains. the bending mode frequencies are poorly known. Although
future infrared spectroscopic missions such as the Herschel Space Observatory will
have the sensitivity and spectral resolution to detect such modes. further laboratory
studies will be required before astronomical identification of long carbon chains can
be secured.

3,5 Polycyclic Aromatic Hydrocarbons

The most interesting feature in the spectrum in Figure 8.15 is the 14.84-um feature.
corresponding to the Q branch of the 114 of benzene (Cal-16) (Fig. 3.19). Benzene is
known to have 20 vibrational modes. but only 4 are infrared active (v.1 at 14.3374 pm,
on at 3.281 ,um, 1:13 at 6.739 um, and v14 at 9.631 lrim). The U4 bending mode. the
strongest of the four. corresponds to all H flapping in the same direction from the plane
of the aromatic ring. The detection of benzene in AFGL 613 suggests that aromatic
molecules can be efficiently produced in the circumstellar envelopes of evolved stars.
Polycyclic aromatic hydrocarbon (PAH) molecules are benzene rings of spl-
hybridized C atoms linked to each other in a plane. with H atoms or other groups
saturating the outer bonds of peripheral C atoms (Fig. 8.20). PAH molecules can be
divided into two general classes: compact PAHS where some C atoms belong to three
rings (e.g.. pyrene Ciero) and noncompact PAl-ls where no C atom belongs to more
than two rings (e.g.. naphthalene CloHs)-

. . .— . —.—
CsHs synthetic spectrum
FLIFC

0.95

Figure 8.19
ISO SW5 spectrum of AFGL 618 showing the v4 bending mode of benzene (Cemieharo e.- at
2001.11”. 546. L123).
 276 Vibrational Spectroscopy of Palyammi'c Molecules

Pericondensed Catacondensed

H H H H H
H H H
H

H H H H
Naphthalene Phenanthrene
CIOHB CHHlD

H
H H H HH H H
H H H H
H H
H H H H H
H H H H
,——A—£r3=fl

H H H H H H
Petylene Benzo(ghi)perylene Tetraphene
Conn ann CtaHiz

H H H

H H H H H H H
H H H H
H H H
H H H H H H H H H H H H H H

Antanthrene Ovalene Pentaphene Pentaphene

szfliz CJZHH C22Hu CnHu

Figure 3.20
Examples of simple PAHs (adapted from Salama I999. in Solid Interstellar Matter: The ISO
Revolution, eds. L d‘Hendeeourt et al., EDP Sciences. p. 65). Although the CC bonds are shown
as alternate single and double bonds in this schematic. the electrons are symmetrically distributed
among all C atoms. and all CC bonds are largely equivalent.

The interest in PAH molecules as a possible constituent of tlte ISM began with
the suggestion that they could be responsible for the infrared emission featum
(Section 12.1). Small, neutral PAHs are primarily excited by UV light. as laboratory
measurements show a sharp cutoff in the UV with little absorption in the visible. If
present. interstellar PAHs could contribute to the energy balance of the ISM through
 Exercises 277

the absorption of diffuse starlight. Absorption of UV photons results in a rapid

redistribution of the photon energy among the vibrational modes of the molecule.
In a low-density environment where collisional de-excitation is not possible. the
molecules undergo spontaneous de-excitation via infrared fiuormcence. leading to
emission features in the infrared. The absorption of diffuse UV light can also lead to
the ejection of electrons through the photoelectric effect. which can contribute to the
heating of the interstellar gas.
PAHs are thought to be formed in the outflows from carbon stars in a process
analogous to soot formation in combustion processes. The first aromatic ring. benzene
(Cfiflg), is formed from acetylene (Section 8.1). the most abundant molecule in C-rich
circumstellar envelopes after H: and CO. PAH molecules can be formed by repeated
radical formation due to H abstraction and addition of hydrocarbons (Section 14.5.4).

3.6 Summary
Astronomical spectroscopy of the vibrational modes of molecules is the result of
advances in infrared technology and the ability to place infrared telescopes in space.
Although ground-based telescopes can observe some stretching modes of molecules.
most bending modes lie in the mid and far infrared and can only be observed from
space. This field of study was opened by the ISO satellite and will be further expanded
by the upcoming Herschel and SOFM missions.
As the number of atoms increases. the number and variety of vibrational modes
increase rapidly. The identification of large (e.g.. bio-) molecules through vibrational
spectroscopy is therefore not trivial. While high-resolution rotational spectroscopy
can definitely identify a specific molecule. this is not always the case for vibrational
spectroscopy. Usually laboratory studies have allowed the classification of spectral
regions as being attributed to vibrational modes originating from a certain functional
group.

Further Reading

For a quantum mechanical treatment of the spectroscopy of atoms and molecules, see
Bmath. P. 2005. Spectra ofAromr and Molecules. 2nd edition. Oxford University Press.
Conley. R. T. 1972. Infrared Spectroscopy. Allyn and Bacon. Boston.

Exercises

1. The linear molecule C02 has three vibrational modes. Which of the three is not
infrared active?
2. The methane molecule has a tetrahedral structure. Do you expect it to have a perma-
nent dipole moment?
 9
Molecular Excitation and
Abundance Determination

In order for a molecular rotatiOnaI or vibrational transition to occur in emission.

the molecule first has to be excited. Interstellar molecules can be excited either
by collisions with both neutral (e.g.. H2) and charged particles (e.g.. electrons).
or by absorption of background continuum radiation. The most common sources
of background radiation are dust emission and the cosmic background radiation.
Because the kinetic temperatures in molecular clouds are low. collisional excitation is
generally limited to excitation to within the rotational state in the ground vibrational
state. Infrared photons provided by warm dust, on the other hand, can radiatively
excite a molecule to a vibrationally excited state. which when decaying to the ground
vibrational state. can cascade through the rotational ladder and emit a series of
rotational transitions.
Tire firsr step toward an understanding of the chemical pathways to the forma-
tion of molecules in space (which will be discussed in detail in Chapter 14) is an
accurate determination of the abundance of various molecular species. The strength
of observed spectral lines must be translated into population densities through radia-
tion transfer, depending on whether the line is optically thick or thin. The population
densities of these excited states are then used to infer the total molecular abundance
through an excitation analysis.
In some cases. the observed abundances of molecules containing isotopes of ele-
ments deviate greatly from their respective atomic isotopic ratios. Such anomalies can
be understood as the result of chemical isotope fractionation under low-temperature
conditions (Section 9. l0).

9.1 Partition Functions and Thermal Distribution

The abundance of molecular species can be determined from the observation of a

single uansition if the absorption coefficient and the pepulation distribution of the
molecule are known. In LTE. the population density in any molecular excited state i
is given by the Boltzmann equation (eq. 2.38):

91 — fle-Er/H‘ (a!)
"o 80
279
280 Molecular Excitation and Abundance Determination

where E,- is the sum of the electronic. vibrational, and rotational energies of the State
no is the population density of the ground state (i‘ = 0). and g.- is the degeneracy oi
state i'. By summing over all excited states. the total molecular density (HT) is given by
m
n _ .
"r = E9 Z 8:3 E""- (9.2}
0 i=0
By defining the partition function Z(T) as
W

20') = Z grehz’ffl- (93)

int]
and making use of eqs. 9. l, 9.2. and 9.3, we have an expression relating the populgficm
of one state (14,-) to the total density of the molecule:

_ "r
__ 2008i-e
—t:.-/kr .
"r (9.4)

For polyatomic molecules in the ISM. the populations of the molecules in excited
electronic states are very small and only the electronic ground states need to be
considered.
If we neglect the interaction between vibratiOn and rotation. the partition function
can be written as the product of vibrational and rotational partition functions. In the
harmonic-oscillator approximation. the vibrational partition function has a simple
form:
29mm) = (I __ e—hv..-'ET) d1(1_ e-hvzlkadzu _ g-*V3/*T)-d3 _ . . _ (9.5)

where u,- are vibrational frequencies. and d., d2, d3. . . . are the degrees of degeneracy
of vibrations v1. vi. 113, . . . . respectively.
The formulae for the rotational partition function are different for linear, symmu-
ric top. and asymmetric top molecules. For diatomic and linear polyatomic molecules.
the rotational energy levels can be assumed to be those of rigid rotators and the par-
tition function is therefore
CD

2, = 2(21 + t)g,e-"”JU+'J/”. (9.6)

J=D

where g, is the nuclear statistical weight At high temperatures where H" >> 113.
the rotational levels are closely spaced together and the summation in eq. 9.6 can be
replaced by an integral:
a:

241'): g f e"'5"(J+')/”d[hBJ(J + l)/kT]

0

z E, (9.?)
I13
where the g; are assumed to be independent of J and have values of l.
 9.3 Excitation ofMolecules 281

For symmetric and asymmetric tops where there is more than one rotational
constant,

7r H3
zr:———,
() ”C(h) .
(98)

where A. B. and C are rotational constants along difierent principal axes (eq. 7.18).

9.2 Deriving the Rotational Excitation Temperature

When several rotational transitions are observed. either in emission by nun/submm
observations or in absorption from vibrational—rotational transitions in the UV!
optical/1R. the excitation temperature can be derived by fining the derived column
densities by the Boltzmann equation. From eq. 9.4, we have

ln( NJ )=ln (15—) J9”). (9.9)

2r +1 2,0,) M,

where NJ is the column density of the molecule in the J rotational slate. N, is the
total number density in the rotational ladder. and T, is the excitational temperature
of the rotational ladder. In the case of a vibrational—rotational transition, N, would
correspond to the total number density in the vibrational state. If the excitation
temperature is a constant, eq. 9.9 is a linear equation. By fitting a straight line to a
plot of In (NI/(2.! + 1)) against E(J)/ k, we have a slope of — 1/ T, and an intercept
of ln(N,/Z,(T)). Making use of eq. 9.6. we can detennine both the excitation
temperature T, and the total population.
If the rotational transitions are observed in absorption against a background
continuum source (Section 7.5). the derived excitation temperature would correspond
to the average temperature of the molecule in the diffuse medium along the line of
sight. If the lines are seen in emission, T, would correspond to the average temperature
in the emitting volume. Depending on whether the molecule is excited by collision
or radiation. T, would correspond to either the kinetic or radiation temperature. If
the plot of eq. 9.9 is not well represented by a straight line, there must be significant
variation in temperature or excitation mechanism within the emitting medium.

9.3 Excitation of Molecules

As in the case of atomic transitions. the population of the initial state of a molecular
transition can be detertnined from the strength of the line, either in emission or in
absorption. For the sake of simplicity. we will use the case of a rotational transition of
a diatomic molecule as an example. The spontaneous emission (Einstein A) coefficient
232 Molecular Excitation and Abundance Determination

from the rotational state J + l to J for a diatomic molecule in a '2+ state is

A”: fl _
sin-3 21,- +3

=0. 4 1001"" 3( u )2 11+! (9.10)

31( l ) ldebye 2Jj+3 ‘

where p. is the permanent dipole moment of the molecule, usually expressed in units
of debye. For the C0 molecule. p. = 0.110 debye and eq. 9.10 gives a value of
A = 7.2 x 10—3 s’I for the l —r 0 transition of CO. Since this transition rate is [6
orders of magnitude lower than the Lyar transition of H. the CO molecule is easier to
excite under interstellar conditions.
The conditions that are required to excite the J = 1 — 0 line of CO can be
estimated by the critical density, which is given by eq. 5.126:

_ AID
"c - —Cto - (9.11)

From eqs. 5.121 and 9.10. we can see that

1
rat or vapzT ’2. (9.12)

For an assumed value of Cw = 2 x 10‘'2 cm3 s". the critical density for the CO
I = l — 0 line is ~ 4 x 104 cm‘a'. Assuming that the collisional cross sections do
not vary greatly between different molecular line transitions. a molecular line with a
larger dipole moment would require a higher density to excite. For example. the CS
molecule has a dipole moment of 2.0 debye, so the J = 2 — I line at 97.981 01-12 has
a spontaneous decay rate of A = 1.7 x 10—5 s". much higher than that of the CO
I = l — 0 line. The CS line therefore requires higher density (> 10‘5 cm'3) to excite.
and can serve as a uaeer of higher-density gas.
In radio astronomy. it is common practice to define an excitation temperature (7,.
eq. 2.33) to represent the papulation ratio of two states

ft = fl;"”fii”"w, (9.13)
"1' 31
where g = 2.! + l. in high-density regions where rim2 > nc. the populations of the
rotational levels are determined by collisional processes. so '1", will be the same for
all states and equal to the kinetic temperature of the field particles (mainly molecular
hydrogen). In this case. the molecule is said to be rhemralized.
For far-infrared lines where the frequency is high. eq. 9.12 suggests 11131 '1'”
critical densities are also high. This means that the population distribution of the
lowest rotational states is ofien subthennal (1"I < Th). If the dust and gas tempflalllfls
are similar. then the line can appear in absorption against the dust continuum (Fig. 9. l )-
 9.3 Exci‘ration analecules 233

Wavelength
[Ocm lcm Imrn IOOum [Oym Iym
'°’IfiFlTl
[0 III] |——— [0 I]
[0 I] [-— [N In]
[C u]

Sgr A West 1
10‘ __ Central 40"

COJ=16—)15
manning—)5

105‘I _

E-
E
'2
3
5
E
102 —

l0 —'

I I J L l J l
[0’ IO” 10" IO” 10’3 [0” l0”
Frequency(Hz)

Figure9.l
A schemaLic spectrum showing both line and continuum emission in Sgt A. The continuum
at high frequency (v > 10” Hz) is due to dust emission whereas at low frequency (v < 10”
Hz) it is due to flee flee emission. Far-infrared lines (such as the OH lnmJ = 5/2 — 3/2
at 119 um) can upper in absorption againsi the dust continuum (adapted from Genzel er al.
I985.Ap.f,191. 766).
284 Molecular Excitation and Abundance Determination

Lower-frequency lines in the m and submrn are easier to excite and will appear in
emrssron.
In general the TJr are different for each transition and their values have to be
determined by solving the equation of statistical equilibrium. Substituting eqs. 9.13
5.3, and 5.9 into eq. 5.15, we have '

2
av .-= ( 1— 9 "W”- ) fl(
g} C )A--lj¢lr .
31'“): (914)

Making use of eq. 9.10, we obtain

_ _ all/tr, 3" 3 V 2 J-+1

r
“”0 e )(Mc)'u'2J-+t¢”'
J (9'15)
The optical depth of a line is therefore

Brr3v J-+l
r = n- l—e’h“""Tl
" f ’( ) 3r": “NJ-+1“ d.‘
(———) 2
(9'16)
If Tyr = 100 K and (til, is given by a square profile with a width of Ikms", then
av has a value of 8.] x 10‘” cm2 for the J = l —> 0 transition of CO. Assuming
n he = 1 cm 3. the optical depth across a molecular cloud of size 0.] pe is 95.
In LTE. the population density in each level is related to the total molecular
abundance by the partition function. Making use of eq. 9.4. we can relate the optical
depth to the total abundance:

3H3IJ J-+l gs .
ru: ( 1— e 4'"!ka ) (—)
3hc u 2-—’—-—-—’—
2Jj+IZ(T)¢”e Em]
J "T d.5 (9.11 )

From eq. 9. l? we can see that the strength of the molecular emission line is
inversely proportional to the partition function. This is because a large partition
function means that the population is distributed over many different rotational levels,
therefore reducing the number taking part in one specific transition. From eq. 9.6. we
see that at a fixed temperature T. Z is larger when the rotational constant B is smaller.
A massive molecule with a large moment of inertia will have a smaller B (eq. 7-5)
and a larger 2 and therefore weaker individual lines. This effect is in part responsible
for the difficulty in detecting biomoleCules through their rotational transitions.
For the J = l —> 0 gmund~state transition of a diatomic molecule. .11 = 0. 31- = l.
and E_,- = 0. therefore

t”: (he-mm.) (2‘2) 2 ”IE—Q (9.13)

3a.: 20')
 9.4 Deriving Molecular Abundancefrom Line Observations 235

The total molecular abundance can therefore be derived once the optical depth is
known:

_ 3hr: 20;) 1 r.
[HT G's—(31W) #2 (Fem/”1) $3
3ckT, ) l ( l ) 1,,
a -— —-——— —.
(3,!sz #2 l _ e—hulkT, ¢v ( 9.19 )

assuming 2 = kT/hB (eq. 9.7).

9.4 Deriving Molecular Abundance from Line Observations

In a molecular cloud with plane-parallel geometry and constant excitation tempera-
ture. the observed line brightness temperature can be derived from eq. 5.133:

r,, — TBG = (T, - TBG)(1— 5'“). (9.20)

if the frequency of the transition is low enough to satisfy the Rayleigh—Jeans approx-
imation. If the line is optically thick (t >> I), then the line temperature above the
continuum is

Tb " Tao = T; 736- (9-21)

In this case, the excitation temperature is given by the measured brightness temper-
ature of the line. If the molecule is thennalized at the kinetic temperature (T1 = 7}).
then the kinetic temperature can be directly obtained from observations (Tk = Tb).
If the line is optically thin.

Tb _ TBG = (TI _ THC)“:

_ 31’3" ll 2 2"
— [(T; — TBG)"j¢'v (a?) J +1
+1 (I — e —:w.rtr, )dS, (9.22)

where we have made use of eq. 9.16. Since v changes only slightly over the profile
of the line. we have an expression for the integrated line flux above the continuum by
integrating eq. 9.22 over frequency:

[(Tb — T30) d1)

.4 31731) J + l
= (r, — rm) (1— e mm) u” (3"?) 2} + I In} d:. (9.23)

Where f nj ds is the column density of the molecule in state j .

In the case of CO, the rotational transitions of 12C0 are generally optically thick.
If the ”‘CO line is Optically thin, then the kinetic temperature Tk obtained from I2C0
286 MoleCular Ercttarion and Abundance Determination

measurement can be used in the ”C0 measurement to obtain the total column densi
of the molecule (f :11 d5). In the example of the ground-state (J = 1 -> 0) husidot:
the total column density of the molecule can be obtained with eq. 9.18; '

_ u 31:3 1
fa. ‘ Tm) 4" = (T: - Tm) (1— e M”‘) “2 (37:) 2—5.; [WS- (924:
Using eq. 3. [4, we can relate the observed antenna temperature (T4) to the brightness
temperature (Tb) and therefore derive the C0 column density from observations.
Provided that the C0sz abundance ratio is known, the total mass of the molecular
gas (MHZ) can be obtained.
We should note that the COM; abundance ratio may vary significantly in differ-em
environments. This ratio is dependent on both CIO and OIH ratios, and both are
functions of metallicity. Consequently, the COIHZ ratio in galaxies of low metallicity
may be much smaller than the normal value in the galactic ISM.
At submillimeter wavelengths. the Rayleigh-Jeans approximation is often not
valid and eq. 5.133 can no longer be used. By rearranging eq. 5.132. we have

1 1 l I _
[er-vim _ l _ chum-,5 _ I] — [eta/k1; _ l _ elm/um _ I] (1“9 '1 (9-25)
If we define

._ l t k
TR = [elm/k1}. ._ 1 " ehv/kTm _ I] (E) (9'26)

as the observed radiation temperature, then

hv l l _
T; = (T) [e_——-h|’fkT.
_ l -— e——————hv/”m
_ I] (1— e I). (9.27)

By rearranging eq. 9.27. we can solve for the excitation temperature

ht)
= __ H"n I _I l
.23
T‘ k [In [1+(hUU—e") +elrv/kTaG— I) ]] (9 )

For an optically thick line (1' > > I), the excitation temperature can be directly derived
from eq. 9.23. We note that eq. 9.28 is the equivalent of eq. 9.21. without using the
Rayleigh-Jeans approximation. If we apply eq. 9.28 to the J = l —> 0 line of C0.
which is usually optically thick, we have
—I
T, = 5532l1n[l
_ 5.532
______
+ (manta-roam)“ , (9.29)

where we have assumed it = l l5.27 I2 GHz and T35 == 2.? K. Therefore. by observing
an optically thick line alone. we can determine the excitation temperature of the
transition. If the excitation of the molecule is dominated by collisions, then T; = Ti
and the kinetic temperature of the gas can be obtained.
 9.5 A Tho-Mel Molecule under Collisional Excitation 28?

Since the 12CO line is optically Illicit. it is not suitable for abundance detennina—
tions. The column density of C0 can be more easily derived from the optically thin
l3CO line. By making the assumption that the excitation temperature is the same for
12CO and I3co and v(‘2C0) as v(”CO). we have
T;(I2C0) ~ I _e—t('zC0)
—— ~ —. .30
r§(|3C0) 1— e-'<”C°) (9 )
From eq. 9.30. we can find an expression for the optical depth of 13C0:
T'UJCO)“ _ e—r('2CO))
r( ”C0) z—I n t—J—-———
T;(12C0) ( 9.31 )

Substituting eq. 9.2? into eq. 9.31. we have

em ,. 1 1 T;('3CO)(1— e-"”°°’) 1 1 -1
fl h- n _ hv(nCO)(l -— e-rt'ml) eta-*1". — l — ehv/tTne — l
To(I3CO) l -I
e—i 1--"—— -——————o.14s . 9.32
nI 5.32 [(eS-JZIT. — 1) l ( )
Substituting eq. 9.32 into eq. 9.19 and making use of the excitation temperature
derived from 12C0 (eq. 9.28). we can obtain the column density of 13'CO from the
observed line radiation temperature.

9.5 A TWO-level Molecule under Collisional Excitation

The formulation in the previous section represents only the simplest case. where
the molecular column density is derived from an optically thin line under plane-
parallel geometry and the molecule is in LTE at the same temperature in every
part of the medium. In reality. the derivation of molecular abundance from infrared.
submillimeter. and millimeter-wave observations must take into account many other
factors. including excitation, optical depth effects. and source structure and geometry.
In this section. we will consider the effect of collisional excitation.
in a two-level system where the excitation is dominated by collisions. the popu-
lation of the upper to lower state is given by eq. 5.125:

n C
fl;=__H2'2 ___1c _ (9.33)
"1 AZI 14.13?"

In contrast to an ionized region where electrons are the field particles responsible for
the collisional excitatioa of atoms and ions. H2 is assumed to be the dominating agent
Molecular Excitation and Abundance Determination

in the collisional excitation of molecules. From the definition of excitation "3mm-

ture (eq. 9.13), we have the following expression for the excitation temperature fol. a
two-level molecule under collisional excitation:

T1 = —————-———-———-’
TI: (9.34)

kT
l+(fi)ln(1+,,—’jf;)
where he is the critical density as defined by eq. 5.126:

__ ‘21
"c — C21. (9.35)

For the co J = 1 —+ 0 transition. A = 7.4 x 10-3 s-1.c2.zto-1° cm-3 s"_ and

rat @740 cm‘s.
At high densities (nH2 >> nr).

-|
ka) n
T1 a Tkl: l + —-—
(hv -—‘—
(”H1)] . ,
(936)

and the excitation temperature approaches the kinetic temperature. Under this eon-
dition. we say that the molecule is themialized. From eq. 9.35 we can see that a
transition with low A value will have a low critical density and the molecule is man:
easily thermalized.
By rearranging eq. 9.33 and making use of eq. 5.123, we have

EZ=£Ze'h”/Hl _____._l

"I 3| l+ fl;

_ a; ‘ I 37
_(n[) (Hi),
flu; (9' J
where (Hz/HI). is the population ratio under thermal conditions. At low densities
(RH2 << inc),

'2 z (2). (IL) . (9.33)

"I n. "C

We can see that the upper state is underpopulated in comparison to the case ofthermal
distribution. and we call this excitation condition of the molecule subthennal.
Under optically thin conditions. the integrated line flux is

r. = f f Mud v. (9.39)
 9.6 A Two-Level Molecule under Collisiona! and Radiative Excitation 289

Making use of eq. 5. l l. we have

hv
FL = ——n2A2. de. (9.40)
4rr

Substuting eq. 9.3? into eq. 9.40. we have under high-density conditions

FL= :1_vAn_8_2£ hurtinfnldv, (9.4!)

IT 81

whereas under low-density conditions

F: Ecufle-"v‘m f mnflzdv. (9.42)

L 4n g.

So for a thermalized transition, the line strength is directly proportional to density.

whereas for a subthennal line. the line strength is proprotional to density squared.

9.6 A 'I‘wo~Level Molecule under Collisional and Radiative Excitation

In the case of optical emission lines. the effects of background radiation can generally
be ignored. However. this is not the case for molecular emission lines. Molecules
undergoing rotational transitions in the mm or submm wavelengths are embedded in
dust clouds. which emit a strong comlnuum in infrared and submm regions (Chapter
l0). Even in the absence of a dust continuum. the cosmic background radiation
is always present. providing radiative excitation for the molecule. The equation of
statistical equilibrium. including the radiative terms. is given by

fll(flH:C12 "' Blzj) = n2(nH2C21+ lej + All) (9.43)

(eq. 5.148). In general. the solution to this equation varies with position in the cloud.
in response to changing environmental conditions (1'). "H2. j. etc.) and the value of
the local average intensity integrated over the line (i. eq. 5.2) has to be determined
from a solution of the dust continuum radiation transfer equation (Section I032).
Assuming that the molecule is immersed in a dust cloud of uniform temperature.
or that the only source of radiation is the 2.7-K cosmic background radiation. the
average intensity can be approximated by a Planck function of temperature T50:

- 2hv3 1
J = c—zem—l, (9.44)

where v is the uansition frequency of the molecular line. In deriving eq. 9.44. we
have made use of eq. 5.2 and assumed that the intensity of the background radiation
is constant across the line profile. Substituting eq. 9.44 into eq. 9.43 and making use
of the relations between the Einstein A and B coefficients (eqs. 5.8 and 5.9). the
relation between the collisional excitation and tie-excitation rates (eq. 5.123). as well
290 Molecular Excitation and Abundance Determination

as the definition of excitation temperature (eq. 9.13), we can derive an ”Minn

for the excitation temperature for a two-level molecule under the combined effect of
collisional and radiative excitation:
4“ hv/ItTk

e
—hv/kT, _
-e
-4vun fflfiiijEEiE;fli___ - (9.4
A21 + flit—1 + "Hzczi 5)
Making use of the definition of the critical density (eq. 9.35). eq. 9.45 can be rewrit—
ten as
:52 (“.1ng
elm/tr, = elm/H". an: 3‘;7"I:<:—i (9 4-5)
u; k .

71.12 + en‘HIEO-l

or
n" (”firm
hv hv r} W
1727:?” vat—*—
I 12;; -
k "r + e v 30—1 (9-47)
At high density (in >> '1‘), eq. 9.46 reduces to T, = Ti and the line is themalized.
At low density (n < < nc). TJr = T55 and the excitation of the molecule is dominated
by radiation excitation. This behavior of the excitation temperature is iilusuated in
Figure 9.2 for molecular transitions of three different critical densities.

I _' l '

IOcm‘3 i

:1: 100cm"
____----d‘
8
In"
- ""
' n = [000 cm'3 _‘

J I l l
5000 "3,000 l5,“
"H, (cm-3)
Figure 9.2
A plot of the excitation temperature as a function of density for a molecular transition II 1C0
GHz with nc =10. 100. and 1000 cm". The kinetic and the background temperatures an
assumed to be 50 and 3 K. respectively.
 9. 7 Optically Thick Lines and Non-LTE Population Distribution 291

if the dominant background is not the cosmic background radiation but a dust
continuum, then the local radiation field J will need to be determined from the solution
of the dust continuum radiation transfer. If the dust temperature can be assumed to
be constant. then at leasr the angular extent of the dust continuum source has to be
included in the calculation of .i. For a dust continuum background of ~ 20 K. the
spectrum will peak at ~ 150 um or 2 THz. Many light molecules have rotational
transitions at terahertz frequencies, and radiation interaction becomes a significant
factor in the excitation of the molecule. If the molecular cloud lies in front of the
dust continuum source. the line can appear in absorption against the dust continuum
(Fig. 9.1).

9,1 Optically Thick Lines and Non-LTE Population Distribution

In the previous section. we have considered only the contribution of a radiation
background to the radiative u-ansition rates 3”- and B}, of the molecule. However,
a molecule can also be excited by line radiation emitted by a neighboring molecule of
the same transition. If this self-absorption rate is significant. the line is considered
to be optically thick. An optically thick line can be the result of high molecular
abundance. strong transition rate (the AU coefficient). or high excitation (high density.
high temperature, or strong radiation background). Examples of optically thick lines
include those of I2C0 and the ground-state transition of H20. The observed strengths
of these lines can only be interpreted with the solution of the radiation transfer
equation.
The problem of molecular line transfer can be set up with the following steps.
First the energy levels and transition probabilities (A,-j) of the transitions are tabulated.
Collisional cross sections of all the transitions. including both by neutral (e.g.. H. He,
H2) and charged (e.g.. electrons) particles. are needed to calculate the collisional
excitation and etc-excitation rates. The degree of contributiOn to the total collisional
rates by charged particles is obviously dependent on the degree of ionization (1,). For
example. in photodissociation regions (PDRs. Section l4.3) the relative abundance
of electrons is close to that of C. Given the fact the electronic cross sections are 3-4
orders of magnitude larger than those of H2. electron collisions are important even in
low ionization environments.
A radiative background consisting of the 3-K cosmic background and any dust
continuum should be included to calculate the stimulated emission and absorption
rates. Assuming adensity and temperature (Th) distribution, the equations of statistical
equilibrium can be set up. Since this is a system oflinear equations. the solutions can
be found by inverting a matrix. \thh the solution of the population distribution. the
source function (eq. 5.12) can be found at each point in space. The equation of transfer
is then solved under the assumed geometry. From the solution. the mean intensity (J)
for each line at each point in space is added to the absorption rates in the statistical
equilibrium equations (Section 5. [5). The population distribution is then recalculated
and the process is repeated until convergence is achieved.
in a moving medium (e.g., a collapsing molecular cloud or an expanding cir-
cumstellar envelope), it is common to adopt the “large velocity gradient" (LVG)
292 Molecular Excitation and Abundance Determination

5o_ I l I T fl ‘
. C0140 5'0_C02—->l

g 3.0 - —I g 10 _
Flt F5

LO - -* l.0 —

_l I_ ; I _L I _L I I I
-4 -2 0 2 4 —4 -2 0 2
Velocity (km/s) Velocity (ltmls)

5-0 I I I I I 40 I F 1 T I
4_O_c03-»2 J 3(II-c0443
A 3.0 — _ A
5 =5, 2 0 —
h‘ 2.0 "' '_‘ LI“

LU _ _ l.0 -

0'0 i I 4 g I 7 0-0 ‘ I L I I_ I
—4 —2 O 2 4 —4 -2 0 2 4
Velocity (km/s) Velocity (km/s)

Figure 9.3
Profiles of the four lowest rotational transitions of C0 in an expanding circumstellar envelope
calculated with a molecular-line transfer program using the Sobolev approximation. The emission
region of the J = 1—» 0 transition (upper left) is resolved by the telescope beam and shows a
double-peaked profile.

appmximation (also referred to as the Sobolev approximation). Under this approx-

imation. the velocity gradient is assumed to be large enough such that the resultant
Doppler effect will shift the photon emitted in one part of the cloud completely out
of the absorption line profile of a nearby molecule. In this case. the radiation transfer
problem becomes a local one. as photons emitted in each part of the cloud will escape.
Figure 9.3 shows the result of a molecular-line radiation transfer model for
C0 emission in a circumstellar envelope with density (n or r 2) and temperaturc
(1",. or. r ' “2) gradients. Approximately 900 rotational states in three vibrational levels
are included in the statistical equilibrium equation. Because higher transitions are not
excited in the outer parts of the envelope. the efi’ective emitting size decreases Will"
I, to ~ 5” for .I = 4 - 3. When obSerVed with a fixed beam (3 ~ 20”). the higher
transitions suffer from increasing beam dilution effects, resulting in weaker antenna
temperatures. In the J = 1 — 0 line. the emitting region (~ 40") is resolved by d“
beam, resulting in a double-peaked profile (Section 15.7.2).
 9.8 Molecular Abundance by Absorption Spectroscopy 293

-rrrrltrurlrrrlllrrl

T= 1300 Km”: = 3 lO‘cm”

10-19

F,(Wcm 2)

lo—lflrrrnlrrrnl-I-Irrrr

D 10 20 30 40
Jun

Figure 9.4
The CO line flLIIE in NGC 1333-IRAS 4 as a frmetion of the rotational quantum number of
the upper state (Giannini er al. 2001. AP]. 555. 40).

Figure 9.4 shows a fit of 13 CO lines (from J = 14 — 13 to J = 29 —- 28) observed

by ISO LWS in the protesters NGC 1333-1RAS 4 using an LVG model. The high (1800
K) gas temperature suggests that CO is excited by shocks generated by the bipolar
outflows in this object.

9.8 Molecular Abundance by Absorption Spectroscopy

If there is a suitable continuum background. the column density of a molecule can be

derived through an absorption line against this background using eqs. 9.18 and 5.130.
In particular. if lines of two molecular species are close in frequency and can be
measured with the same instrument. then an accurate determination of the abundance
ratio is possible. This applies to the v = 2 — 0 firm overtorre vibrational transition
of CO at 2.3 pm and the v = l — 0 5(0) and 3(1) lines of H2 at 2.22 and 2.12 pm,
respectively. These lines can be observed simultaneously in the K band atmospheric
window with an infrared spectrometer. Since the two molecular species are within the
same absorbing column and therefore likely to have the same excitation temperatures.
the COII-lz ratio can be determined with an assumed ortho to para ratio of H1. The
observed value derived by this technique is 10—3—10'4 depending on the location in
the Galaxy.
Through a combination of absorption and emission spectroscopy, the abun-
dance of many molecular species can be determined in different environments. While
294 Molecular Excitation and Abundance Determination

emission spectroscopy is the most advantageous technique in high-density, high.

temperature regions such as the cores of molecular clouds, molecular abundance in
difiuse clouds is best carried out through absorption spectroscopy. EIarnples Oldies:
results are given in Figure 9.5, which can be used to find out the physical condition
and operating chemical networks in different components of the ISM.

Diffuse cloud Molecular cloud bow-muss protester High-mass [mustar-

(g Oph) (TMC-l) (IRAS 16293-2422) (Orion hot core)
i i i
l | |C0
'04 ' C‘ ICO ICO I
I l I
I C° I l
I I I
so I | |
[0-5 _ N“ I I I“-20

C° l I l "H‘
I I I
CO I I I
104 _ l l ocs: HCN “:3
IOH IIICOOCHa :3 I
u I lCHJOH 2 ICHJOH
g I lCHJOCHJ ",5 |
3_ 1w —
a 5+ :' C2“
CH c
'IHNCO
1 H 3 c1 H
HCOOH I'
2 0H CH‘ | C1 CN |
“g C" III-I 2 COCH
c H NH!
HCN cs : :H’CO C5
crIch3 CH CNso
“- 10" - :HCO* ‘ HC N50 :CszCN CHIC” :HCOOCHJCzrlpn '
CN I HC:N I S“) £28314 HC NEKOZS
I CH C H I CS | H 3
9 ECO. NH ICH
I I0H ’ ’CH,CN0“:ch
I HCN
s II C 3C!"
10' HCN cs ICHZCEH HC1N I HCN I
I I I
ICHIClgf’H new I c,H Icnzco
lHNCO l C” lCH’CHO
10-"l — I C Hell" I I
I I I
I I I
I I I
I I I
10-” l l l

Figure 9.5
An illustration of the diverse forms that common elements such as C. N. O. and so on. can have in the
ISM. The fractional abundances (relative to H) of ions. atoms. and molecules of these elements are
plotted in four different regions of the ISM. The difference in molecular abundance is the result of
different temperature, density, and radiation environmenls of dues: regions. Solid-state forms such as
ices and grains are not included in this diagram (from Wooden, Chernley. and Ehrent'reund 2005. in
Corner: ll. eds. M. Festou. H. U. Keller. and H. A. Weaver. University of Arizona Press. Tucson. 33)-
 9. I0 Isotopic Abundance 293

9'9 OrthofPara Ratios

The ortho state of a molecule is defined as having the larger of two statistical spin
weights and part: as having the smaller weight (Section 7.7). Since the typical energy
separation between the ortho and para states of a molecule is comparable to the
gas and dust temperature in the ISM and much smaller than the energy released in
formation reactions. it is expected that the abundance ratio between the two states will
reflect the equilibrium values at high temperatures. that is. the ratio of their statistical
weights. Since 3 = 21 + l. the usual onho topara ratio is [2(1) + l]/{2(0) + 1] = 3
for spin '/2 sYstems such as Hz.
If a molecule cannot be convened from ortho to para (or vice versa) by radiative
or collisional processes. the two states can effectively be considered as two separate
molecules. In this case. die artho to para ratio at the time of molecule formation will
be preserved.

9.10 Isotopic Abundance

The relative isotopic abundance of elements is an important astrophysical parameter
for it reflects the nucleosynthesis process during the Big Bang (for light elements) or
in evolved stars (for heavier elements). In molecular species. isotopic abundance can
be measured through rotational or vibrational transitions for which the frequencies
of the transitions are shifted as a result of the altered mass due to the presence of
extra neutrons (eq. 7.2). For atomic species. the wavelengths of the recombination
lines of H and He are slightly altered for different isotopes through the change in
efiective electron-reduced mass (eq. 4.3). Other methods include the use of hyperfine
transitions as a result of different nuclear spin of the isotopic species. as in the case
of ”C“ and '3C“(Sectior1 5.4.2).
Observations of the Sun and the atmospheres of planets have generally yielded
a consistent set of values for the isotopic ratios of elements. The most widely used
indicators of isotopic ratios are the deuterium to H ratio ('5 0.8 - 2 x 10-5) and the
12Ct'ulC ratio. which has a terrestrial value of 39. However, the isotopic ratios of
interstellar molecules often deviate from these values. When the DCN was detected
in Orion in 1973, it was found to have an abundance of 6 x 10—3 of HCN. much
higher than the cosmic DIH abundance ratio. The high abundance of DCN to HCN
has since been identified as a result of chemical fractionation under low-temperature
conditions.
Chemical fractionation arises from the difference in binding energy between
DCN and HCN. which have values of 2831cm‘l and 3-479 cm‘l. respectively.
This energy difference in temperature is therefore T = AE/k = hc(3479cm" -
2881 cm“)/lr = 361 K. If the molecule is formed with the following exchange reac-
tion (Section 14.5),

HD + HCN .—_~ 1-12 + DCN. (9.4s)

296 Molecular Excitation and Abundance Derenntnarion

then the equilibrium abundance ratio is

[DCNI _ lHD] exp[456 KIT)

[HCN] [H2]
[D]

since HD and H2 also have a binding energy difference of 28] cm" or 4-05 K. For
T = NO K. eq. 9.49 gives a factor of WI between the abundance ratio of DCN to
HCN and the abundance ratio of D to H.
If D and H are in atomic rather than molecular forms. then the formation of DCN
and HCN will be governed by the following exchange reaction:

D + HCN .—_- DCN + H (9.50)

and the equilibrium abundance ratio is

[DCN]
[HCN]
[D]
[H] exp(B6l K/ T). (951)

The effect of chemical fractionation is dependent on the abundance of the other

species. For example, the difference between monodeuterated water and normal
water is 1245 cm". or E / k = 1793 K. which at first glance suggests that in low-
temperature regions HDO could be more abundant than normal water. However. 0 is
more abundant than D by at least a factor of 5. so even in the low-temperature limit
where every D is locked into a water molecule. the HDO to normal water ratio is no
higher than I to 4. Similarly. since 0 is more abundant than C. in the core of dark
clouds where every 13C and '2C atom is in the form of C0, the I3CO to l2C0 ratio,
in fact. reflects the abundance ratio of I3C to 12C.

9.11 Isomers

lsomers are molecules that consist of the same number of atoms of each element
and have the same molecular weight but with different geometric structures. A
common example of isomers in the ISM is HCN and HNC. two linear triatomic
molecules arranged in different order. Similar examples include CH3CNICH3NC
and HCCCNIHCCNCI'HNCCC. Ethanol (CHJCHZOH) has two C, one 0. and six
H atoms, exactly the same as dimethyl ether (CHJOCHJ). but they have different
stmetures and chemical properties.
Known triple isomers in the ISM include the C2H4O family: acetaldehydc
(CH;—CH=O). ethylene oxide (c-C2H4O), and vinyl alcohol (CH2=CH—Oll)
(Fig. 9.6); and the C2H402 family: methyl fen-nate (CHgOCHO). acetic aCld
(CH3COOH). and glycol aldehyde (HO-CH2-—CHO) (Fig. 9.7).
Another example of a molecule that forms isomers is C3l-I. a member oft-he
family of hydrocarbon radicals (CHH) of linear structure. A cyclic form of this radical
 9. I I Learner: 297

H H
Acetaldehyde Ethylene oxide

Figure 9.6
[mm of vinyl alcohol (Turner and Apponi 200i . ApJ. 561. L207).

Flgure 9.7
lsomers of C2H402. All atoms are in the plane of the paper. except the H atoms in the methyl
and methylene groups (indicated by triangular connections) (from Hollis e: at. 2000, ApJ. 540.
L107).
298 Molecular Excitation and Abundance Determination

HJC H HJC H
/ \ /
C=C C=C
\ \
H C= H /C —'0
/ / \
0 0 H
\
H
s-tran: s-cis

Figure 9.8
The trans and cis isomers of the crotonic acid molecule.

(referred to as c-C3H) was discovered in laboratory discharge experiments. The Cyclic

C3H consists of three C atoms in a triangle with the H atom attached to One Comet:
A subclass of isomers is called stereoisorner. in which atoms have similar bond.
ing patients but different spatial arrangements. The terms “cis-" and “trans-” are used
to mean whether a group is on the "same side“ or the “opposite side" of a structure fea.
ture such as a double bond. These are called geometric isomers and they usually havc
different physical properties. For example. cyclopropane (C3146) has a well-defined
plane formed by the three C atoms. and the six H atoms are on either side of this
plane (above or below). If two of the H atoms are replaced by methyl groups. these
two methyl groups can be on the same side (cis) or opposite sides (trans) ofthe ring.
These two isomers have distinct geometric forms (see Fig. 9.8}.
Besides geometric isomers. stereoisomers can also come in the form of optical
isomers. Optical isomers are molecules that are mirror images of each other but cannot
be superimposed on each other. As an analogy. the mirror image of our left hand is
the same as our right hand. and yet we cannot superimpose our left and right hands
together. Such molecules are called chiral molecules. To put it another way. chiral
molecules do out have a plane of symmeuy, whereas achiral molecules do. When
plane-polarized light is passed through an optical isomer. the plane of polarization is
rotated in opposite directions. If it is rotated clockwise. the molecule is known as right-
handed, whereas a counterclockwise rotatiOn is caused by a left-handed molecule. In
organic molecules. chirality is often created by a tetrahedral (er hybridized. Section
1 1.3) C atom bonded to four different groups. For example, every one of the 20 amino
acids (except glycine) can occur as either left or right isomers. with the left isomer
being more common in nature.
As the number of atoms in a molecule increases. the possible number of isomers
of a molecule grows rapidly. C2H2 can be in the forms of vinylidene (HZCC) ”‘1
acetylene (HCCH). C3Hz has six. C4141; has eighteen. and CSHZ has forty-nine possi-
ble bonding arrangements. although not all have energy minima on potential surfaces
that qualify them as molecules. Figure 9.9 shows some examples of the isomers of
C7H2. Theoretical calculations suggest that the ring-chain (labelled l in Fig. 9.9) is
the most stable isomer of the molecule.
 9.“ homers 299

Ground State 0-09 ‘V

3.3 D 3.9D 2

2T
0.96 eV 3
3.1 D

° 0.91 eV 5
5 6.5 D

7 ' 0.74 eV 3
2.3 D
0.74 eV
5.2 D .,
9
Figure 9.9
Some possible low—lying isomers of C1H2: filled circles are C. open circles H (adapted from
Thaddeus er al. 1998. in Faraday Discussions. 109. 121).

The rotational Spectra of many isomers can be calculated to high accuracies.

therefore allowing the laboratory identification of these transitions. Figure 9.10 shows
examples of the low-lying rotational states of the bent chain carbene isomer of Cal-I;
and the transitions measured in the laboratory. The existence of bent carbene suggests
that ringer isomers of C6H2 may also be detectable in the laboratory or in the ISM.
The different abundances observed in isomers contain important infomation
on the chemical pathway leading to their formation. For example, methyl fomtate
(CH30CH0) has a C—O—C backbone and is widely observed in the ISM. Its isomers
include acetic acid (CH3COOH) and glycolaldehyde (CHZOHCHO); both are found
to be much less abundant. The low abundance ratio between acetic acid and methyl
female suggests that the C—C—O backbone is much less likely to form titan the
C—O—C backbone. Since acetic acid can react with NH; to form the amino acid
glycine (NHZCHZCOOH). the isomeric abundance therefore has implications on the
300 Molecular Excitation and Abundance Determination

H C
HC T \Cé'¥
26
A. |' I.
II\ I
C \_,’c
H/ \C/

[20"

74

74‘
by t Ae
e
ELI
S
,- ‘2

0|- -0

Flgure 9.10
A number of the rotational transitions (shown in the energy diagram) of bent qu (top left)
have been detected in the laboratory. Ab initio calculatiOns suggest that other isomers of
CfiHZ. such as the two silt-numbered rings shown on top. may also be possible (adapted from
McCarthy and Thaddeus. 2002, tip}. 569. L55).

creation of glycine in space. The other isomer is glycolaldehyde. an example of

a monosaccharide (simple sugar). Munosaccharides are aldehydes or ketorles that
have two or more hydroxyl groups and have the empirical formula of Cal-tho...
Monosaccharides can connect with other monosaccharides to form polysaccharidc
chains. These sugars together make up the carbohydrates class of biomolecules.

9.12 Conformers

Many simple molecules (such as H20) are classified as asymmetric rotetors because
of their nonequal principal moments of inertia. As the number of atoms increases.
the number of geometric arrangements also increases. Hydrogen peroxide (HOOH)
has a nonplanar equilibrium structure. but the barrier to rotation about the 0—0
bond is about 380 crrt‘l to the trans form and 2400 cn't'l to the cis form. HOOH has
 Ererciscs 301

nonplanar structure at equilibrium. Planar forms are transition states and do not exist.
Such different spatial arrangements of a molecule generated by rotation about a single
bond are called conformation. and a specific conformation is called a confanner. The
simplest hydrocarbon that can have distinct conformationsis ethane (C2115). ln ethane.
three H atoms are connected to one C atom in a tetrahedral unit (5,193), which can rotate
w.r.t. the C——C bond resulting in different conformations.
If the different conformers have different energies. then the population of the
molecule will be spread over many different energy levels. leading to a large partition
function and wealt individual transitions (Section 9.1). Furthennore. these weak lines
can be overlapped by rotational transitions of other more abundant molecules. making
detection difficult. An example of such a molecule is glycine (NH2CH2C00H). the
smallest amino acid. A search for glycine will necessarily rely on using transitions at
high frequencies. as well as avoiding spectral regions with high density of lines.

9.13 Summary
Our ability to observe a large number of transitions of a molecule over a range of
frequencies has made possible an accurate determination of the environmental con-
ditions (kinetic temperature. radiation background. and molecular hydrogen density)
in the surroundings of the molecule. as well as the abundance of lhe molecule. This is
achieved by fitting the observad line strengths by models produced by a self-censistcnt
solution to the equation of radiation transfer and statistical equilibrium, provided that
the molecular consmnts (e.g.. the radiative rates) and the collisional cross sections are
known from either laboratory measurements or theoretical calculations. The compu-
tational power of modern machines allows for the inclusion of hundreds of energy
levels of the molecule. including both the rotational and vibrational states in such
calculations. Molecular-line observations in the mm. submm. and infrared regions
therefore represent some of the most powerful probes to the conditions of the ISM.
as well as determination of the abundance of molecular species and their isotopes.
isomers. and confonners. The measurements of the relative abundance of different
molecules allow the construction and differentiation of chemical models on the syn-
thesis of molecules in the lSM. Such chemical reactions can occur either in the gas
phase or on the surface of dust grains, a subject that will be discussed in detail in
Chapter 14.

Exercises

. A diatomic molecule has a rotational constant of 50 GHz. If there are three times as
many molecules in the J = 1 state as in the J = 2 state:

0 What is the excitation temperature T2.?

0 If the kinetic temperature is [0 K. calculate the departure coefficients ratio bZ/bl.
302 Molecular Excitation and Abundance Determination

0 If the molecule has a spontaneous emission coefficient (A2,) of l0'5 s“ and

the line has a uniform absorption profile over a frequencyr interval of I MEL
calculate the absorption coefficient (av) for this line.

2. Under LTE and high temperature (hB/kT << I), show that the partition function fur
the rotational transitions of a diatomic molecule is
2“"
T = —.
Q( ) hum (E11)

By evaluating the exact partition function of CO at 100 K. show that the expression
above is a reasonable approximation.
3. A two-level molecule is excited by collisions by hydrogen at kinetic temper-am
Ti and density (nH). as well as a background radiation field BU(TBG). Assuming
hv/kT << I, hu/kTBG << 1. flu/k7} << l.deriveanexpression forthe excitation tem-
perature in terms of n”. Tk. T30. and the transition frequency v. The collisional
de-excitalion and spontaneous emission coefficients are C21 and A21. respectively.
/1Q
Interstellar Grains:
Physical Processes

When dark patches in the Milky Way were first observed. they were believed to
be “holes" or “voids" in the distribution of stars. “William Herschel considered the
absence of stars in these voids as the “opening of the Heavens." [t was not until
the 1930s before these objects were realized to be obscuring dust clouds in front of
backgron stars. Even E. E. Barnard. who catalogued many of the dark nebulae we
know today, titled his 1919 paper “0n the dark markings ofthe sky.” He acknowledged
that some of these “markings" could be due to obscuring masses in space, but did not
speculate on the agent of obscuratiOn.
The existence of interstellar dust was finally firmly established from the observa-
tion of varying extinction of starlight in different palm of the visible region. Many stars
en the galactic plane appear redder than expected based on their Spectral types. The
phenomenon of increasing degree of absorptionlscattering at shorter wavelengths is
known as selective extinction. The differences between colors inferred from photom-
etry and temperatures derived from spectroscopy can be attributed to small particles
in the ISM between stars and the observer.
Interstellar dust also manifests itself through scattering. Reflection nebulae are
the result of the scattering of starlight by dust in the ISM. The fact that most reflection
nebulae are blue is the result of stronger scattering by dust at short wavelengths. Since
the efficiency of scattering is related to the ratio of the wavelength to grain size. the
observed wavelength dependence of the scattering process therefore provides limits
on the grain size distribution.
An analogy of these effects can be found in our everyday experience. The Sun
appears redder at sunset because of selective extinction by small particles in the
Earth's atmosphere. Similarly. the slry is blue because short-wavelength photons are
preferentially scattered by both molecules and dust. Pollutants from automobiles or
industry produce haze over our cities. Water condensation on these particles leads to
the formation of fog. Haze and fog are manifesrations of the optical efl‘eus of small
particles in our atmosphere on sunlight.
Evidence for interstellar dust scattering can also be found in the existence of X-
ray haloes around X-ray point sources. The angular size of X—ray sources is extended
as a result of small-angle scattering of X-rays by foreground interstellar dust grains.

303
304 Interstellar Grains: Physical Processes

+11 1

of» .N ------ - ~ His" +9-----91°Eafi'99?°3'!§asphase) ‘

o i .m
A .ARC '0 4"“
P

s
nu _ A
a +a~ ..
$3 Na+'
2 I .GI+K
g ICu IMn IS:
... on 'Ms
H)

'2' —2 t-V
__ .
Cr. IF:
5 E
" Co+lNi
—3
Hum) 'T'
: [02(xm)9 + GIU'ID‘HFI

l a a l I I Jir‘r 1 1 I a .I | r. |.co' _
D 500 IODO 1500
Condensation temperature (K)

Figure 10.1
Gaspphase abundance [XfH] =10th/H) logtfoh. versus condensation temperature for
the diffuse interstellar cloud toward :1 Oph. Data frorn the HST Goddard High-Resolution
Spectrograph are shown as filled squares. and data from the Copernicus satellite and optical
data are shown as filled circles (from Savage and Sembach I996. Ann. Rev. Arte Ap, 34. 279).

The observed underabundance of refractory elements (C. 0. Fe. Si. Mg. S. Ca. Al.
Ni. etc.) in the gas phase suggests that these elements may be condensed into gtains.
Comparisons with observed interstellar abundance of heavy elements with those in
the Sun provide us with clues of the chemical composition of interstellar grains
(eq. 5.15l). It has been estimated that approximately two-thirds of the interstellar
carbon. and most of the silicon and iron, are in the solid form. A correlation between
elemental abundance deficiency in the gas phase and condensation temperature is
shown in Figure l0.l. This provides strong evidence that the missing elements an:
condensed into grains.
Interstellar grains can also be directly detected through their self-emission. If
the grains are large enough to achieve a state of thennodynamic equilibrium after
the absorption of interstellar visible photons. they will self-radiate according l0 the
Planck formula (eq. 2.36) modified by the grain emissivity. From the peak radiation
wavelength given by the Wien's law (eq. 2.56). we can infer the temperature of the
interstellar grains, with typical temperatures in the range of 10 to 100 K. At these
 10.! Interstellar Extinction 305

low temperatures. the peak radiation wavelengths are longer than 30 p.111, beyond
the longest infrared window pennined by observations from the ground. Grains that
are located near stars. for example. as the result of their formation in a stellar wind,
will intercept a larger amount of stellar photons and have a higher temperature. At a
temperature of ~ 300 K. the peak of radiation will be at 10 um. where there exists an
atmospheric window. As a result. it is circumstellar dust that was the first detected in
emission by infrared techniques.
A first indication of the wide extent of thermal dust emission in the Galaxy was
found by IRAS in [932. which mapped 95% of the entire sky in four (12, 25, 60. and
100 um) bands (Section 3.1.1). Also. absolute sky brightness maps at 10 wavebands
(125—240 tun) were made by the Diffuse Infrared Background Experiment on the
CORE satellite in 1989. Both observations are generally consistent with cool (~ 20
K). micron-sized grains in equilibrium with the local interstellar radiation field.
IRAS also revealed a high—temperature (500—1000 K) dust component in the
ISM. which cannot be at thermodynamic equilibrium. This component is explained
by a population of very small grains. which have heat capacities so small that the
absorption of a single UWoptical photon excites the particle to high temperatures
(Section 10.7).
Far-infrared observations by space observatories (e.g.. IRAS. ISO) and
submillimeter-wave photometric observations by ground-based telescopes have now
shown that dust continuum emission is common in external galaxies even to high
redshifts. This suggests that grain formation occurs early in the history of galactic
evoluriOn. and dust is a significant constituent of the Universe.

10.1 Interstellar Extinction

If the intrinsic colors of a star of a particular spectral type are known. the amount of
extinction suffered by the star can be estimated from the color excess. defined as

Ea v=(3—V)-(B-V)o. (10.1)

where B -- V and (B — V)" are, respectively. the observed and intrinsic values of
the color index (Section 3. l . l). The total extinction. A,“ is defined as the increase in
apparent magnitude of a star at wavelength A as the result of extinction:

m.=M.+5Iogd-5+A., (10.2)

where my and M). are. respectively, the apparent and absolute magnitudes of the star
at wavelength A and d is the distance in pc. The wavelength dependence of extinction
(called the extinction curve. Fig. 10.2) can be derived by comparing a star with another
of similar luminosity and spectral type but with negligible extinction. If we write A1711
306 Interstellar Grains: Physical Processes

' ' ' ' j

BD+56 524
Computed R ___ 2 75

U
4AM

-0.2

Ill film")

Figure 10.2
interstellar extinction curves along three different lines of sight of different RV values {from
Cardelli er at. [98114331345 245).

as the difierence in apparent magnitudes at 3. between two stars, then

Ami- Arm; __ AA.— Av

AME-Anny AB—AV

=.- 51-", (no.3)

Era—v
Figure 10.2 shows three examples of the interstellar extinction cune. We can see
that the extinction increases approximately linearly with decreasing wavelength. with
the exception of a peak at 1 ~ 2175 A (Section 12.2).
The ratio of the total extinction and color excess (RV = A1,; /E3-9) is dependent
on the composition and size of the interstellar grains. From eq. 10.3, we have

E _ A
_‘Li = 2‘ _ R1" (10.4)
EB—V EB-V
 10.1 interstellar Extinction 307

Assuming that extinction goes to zero at very long waveleng1hs. we obtain

RV=— EH’] . (10.5)

EB“, A-voo

By extrapolating the observed mean extinction curve to long wavelengths and

assuming that the absorption and scattering obey the small particle approximation.
we find that RV has a value of 3.05 :i: 0.15. While this value of Ry generally applies
to the diffuse ISM. its values are higher in molecular clouds. Figure 10.2 shows
the extinction curves toward three different sources with distinct values of fly. The
observed difference suggests a larger grain size in molecular clouds. which could be
the result of accretion of mantles around the grain core.
The shape of the extinction curve can also be tested by spectroscopic observations
of emission lines. Since the line Iatios of recombination lines are known from theory
(Section 5.1 1). any deviation from the expected ratios is likely to be due to extinction.
Figure 10.3 shows the extinction curve toward NGC 7027. with data points from
llrll—rllllleIIIIIIlllll
EH. - V)IE(B — V)
M

0—Htlines
o—HeIIlines
.2 - — Forbidden lines
' - Seaton (1979]

_4 _l I l l l I I l I 1 I I I I I
0 2 4 6
1"(I-II1'I")
Figure 10.3
Extinction curve toward NGC 7027 derived using fluxes of emission lines in the UV and the
infrared. The solid curve is the standard ISM reddening law for R = 3.2 (from Zhang et al. in
[AU Symposium 209 Planetary Nebulae: Their Evolution and Role in the Universe. eds. Kwok
er al. ASP. p. 319).
308 lmerstellar Grains: Physical Processes

the recombination lines of H 1 and H it and some forbidden lines. With line fluxes
measured from the infrared (e.g.. 150) to the UV (e.g.. IUE), the extinction cum, can
be determined over a wide spectral range. For example. in Figure 10.3, the ttvo UV
points near 1600 A at" ~ 6.25) areden'ved from [Ne w] 2.1602me 1:11:1166511"es
The forbidden lines values are less accurate beeause they suffer from uncertainties it)
the T, and u, used.

10.2 Dust Absorption and Scattering

For macroscopic objects in our everyday life. whose sizes are much greater than the
wavelength of the photons they interact with. their cross sections for light absctrption
are simply given by their geometric cross sections. For a spherical object of radius a
the absorption coefficient (Section 2.6) is given by I

xv = naznd. (10.6)
where nd is the number density. For smaller objects, such as interstellar grains, Where
the a >> A condition is not valid, a dimensionless number Qv(a). called the extinction
eflict‘ency, can be introduced into eq. 10.6 to give

Ku = rrazQ”(a)nd. (10.7)

The extinction efficiency can be separated into the absorption and scattering
components (Section 2.9):

Q”. = Qabs + 95“. (10.3)

where both Qm and Qm are frequency dependent. The value for QM and Q,“ can
in principle be calculated for grains of any size and shape from the complex index of
refraction (Section 5.6)

N=n —ik (10.9)

by solving Maxwell’s equations with appropriate boundary conditions. This method

is generally referred to as Mic theory. Grains in the ISM can be categorized into metals
(n ~ It, e.g., graphite) or dielectrics (k ~ 0. e.g., silicates). Both n and k are generally
functions of wavelength.
For very small spherical grains.

21m )4 N2 — 1 I:
Qsca 3-" E3 J. N2 + 2
(10.10)

27m N2 — l
cm ( i ) (N2 + 2)
2: -4 — IM . (10.11)
 i0.2 Dust Absorption and Scattering 309

where 1M(x) represents the imaginary part of Jr. We see that eq. 10.10 reduces to
Rayleigh scattering (Qm or A4) if N is real and nearly constant. For weak absorbers.
Qabs o: A '. The quantity (km/(1:21“,s + QM) is called the albedo (w). The angular
distribution of photons after scattering with dust can also in principle be calculated
by Mic meory.
The directional dependence of grain scattering is defined by

_ f; 1(0) cos 6 sin 9dr?

10.12
[0" [(6) sin Ede ( )

where 0 is the angle of the scattered photon relative to the incident photon. The angular
distribution of photons after scattering with grains is approximated by the Henyey—
Greenstein scattering phase function (Section 2.9):

[—32
P 9 E—-—————-. (10.13)
( ) (1+gZ-2g c056)“
For isotropic scattering, g = 0 and PG!) = 1. When light is absorbed by a grain.
momentum is transferred from the photon to the grain. When light is scattered, a
fraction of the forward momentum is also transferred depending on the phase function
of the scattered light. We can therefore define a radiation pressure efficiency Qp, as

th 1' Qettt _ SQsea- (10.14)

For isotropic scattering. Qpr 2: Q"). For complete forward scattering where all the
forward momentum remains in the photon. Qt,r = Qabs. For a completely reflective
material (9311:! = 0). Qpr = (i _ g)Qscr
Starting from the optical constants. which can be measured by transmission
through thin films and reflection measurements 0n bulk materials, QM and Q5“
can be calculated assuming a certain size and shape of the grain. However, it is not
certain that optical constants derived from bulk materials are accurate representations
of small (um— or nm-size) particles. Alternatively, We could try to simulate interstellar
or circumstellar grains in the laboratory (Section 13.3) and directly measure their
absorption and scattering cross sections. The challange here is to perform infrared
spectroscopy of the isolated particles.
In the following discussion. we will concentrate on the absorption and emission
of interstellar grains. and we shall ad0pt the approximation

Q “' QoUi'AoY". (10.15)

where or has the value of ~ 1—2 depending on the grain composition.
The amount of grains in the ISM is limited by the cosmic abundance of the heavy
elements that make up the grain. The dust-to-gas mass ratio (til) can be written as

a = L”, {10.16)
p
310 Interstellar Grains: Physical Processes

where A is the atomic mass of the molecular compound. y is lhe number abundance
of lhe least abundant element. u. is the mean atomic weight per H alom, and f is the
fraction of that element that condenses into solid form. For example. for Mgzsio
(A = 140,”, = 3.3 x 10-5. f = Landp. = 1.3),.1; = 3.6 x 10-3.1hecompondjn;
dust-to-gas number ratio is

14 = JLMH. (m
"H 4337039: '17)

where p_., is the density of the grain.

For a = 0.1 pm and p, = l g cm‘3. the dust-to—gas number ratio is [.4 x lo-tz_
The optical depth due to dust absorption along the line of sight is

t = f yrazQundds. (10.13)
The optical depth due to dust absorption can be related to the total extinction (A1)
through the definition of magnitudes (eq. 3.1). Since each magnitude of visual extinc-
tion causes 10“” decrease in visual light.
A; = 2.5 x log(e) x 1';
= 1.036% (10.19)

The near equality between I; and A; makes it very convenient to convert from one
to the other.
We can express the visual extinction due to dust in terms of the H column density
(NH = f ans). the total number of H atoms along the line of sight:

AV -_- 2.5(log e)n—drraszNH

"H

= Loasn—dnaZQVNH. (10.20)
"H
where Q y is the extinction efficiency at V band. Using the dust parameters above and
assuming Q, = 2, we have

Av =10-1'NH. (10.21)
For an interstellar gas density of n" = 1cm". a star at a distance of l ltpc away will
Suffer an extinction of A v = 3 magnitudes.
Figure 10.4 shows images of the dark cloud Barnard 68 at different wavelengths.
The fact that the cloud is progressively more opaque at shorter wavelengths reflects
the opacity function of the dust. By assuming a standard extinction law and intrinSiC
colors of the background stars. one can derive the extinction along the line of sight
of each background star using, for example. the H and K images. Since the column
density is directly proportional to the extinction values, the column density profits as
 [0.3 Dust Emission 311

‘; siiiitt'nt

Figure 10.4
The dependence of dust extinction on wavelength is illustrated in these images of the dark
cloud Barnard 63 (clockwise from top left: 5. V. l. J. H, K). The dustcloud is much less opaque
in the near infrared than in the visible (European Southern Observatory).

a function of distance to the center of the cloud can be obtained. Results on Barnard 6B
are consistent with the properties of a self-gravitating. pressure-confined. isothermal
sphere in hydrostatic equilibrium (Section 15.2).

10.3 Dust Emission

Dust grains are macroscopic particles and their emission spectra are determined by
their temperatures. Since the gas and dusr densities in the ISM are very low, gas
collisions play very little role in the heating and cooling of the grains. The lack of
thermal exchange between the gas and dust components implies that the gas and dust
temperatures are generally decoupled. The gas temperature in an interstellar cloud
is the result of a balance between radiative (Section 6.5) and mechanical (Section
16.1) heating and selfvradiation. whereas the temperatures of grains are primarily
determined by radiative processes: heating by diffuse starlight and cooling by self-
radiation. As a result, the gas and dust temperatures can be vastly different. For
example, in an ionized nebula, the gas temperature is ~ 104 K (Section 6.5). but
the dust temperature is only ~ 102 K. The only exception to the gas—dust thermal
decoupling is in dark clouds, where gas desorption from dust grains plays a role in
the heating of the gas (Section 14.8.1).
312 Interstellar Grains: Physical Processes

10.3.1 Uniform Temperature Case

We begin the discussion of the emission Spectrum of dust clouds with the Simplest
example, an optically thin cloud where the dust temperature is uniform “ember:
in the volume.
in thermodynamic equilibrium, the emissiOn coefficient is related to the abs“?
tion coefficient by Kirchhofl‘s law:

I. = (newsman). (10.22)
where Td is the dust temperature. Assuming that the dust temperature is uniform and
the cloud is optically thin, the flux emitted from a nebula of radius R at distance D
can be obtained by substituting eq. 10.22 into eq. 2.85:

_ wMgastBJTd)
F . (10.23)
v gap, 132

where Mgas is the gas mass of the cloud. We note that for a unifon'o-temperamn,
optically thin dust cloud. the emitted flux is dependent only on the total dust mass in
the cloud and is independent of its volume or dust distribution within the cloud. For
a dust cloud with Mg“ of 0.2 M3, a :01 um. p_. = [gem—3, Q()t = 1pm) =01,
a=1,w=3 x10‘3.Td=100K,a.ndD=lkpc,thefluxatZSumi83m.ly.
For a uniform-density dust cloud. the total entitled flux can also be expressed in
terms of the optical depth through the cloud center (rm). Making use of eq. 10.18. we
can express eq. 10.23 as

rv = 1:192 Ge") 3,,(rd). (10.24)

where 6 = R/ D. We note that eq. 10.24 is the same as eq. 2.84, the solution to the
equation of transfer fora uniform-density sphere with constant source function. Figure
10.5 shows the SED of the dark cloud 1.16893 fitted by eq. [0.24, with I‘d = 13 K.
0 = '12 arcsec. and I," = 0.0] (M200 urn) 2. Since rm ~ 0.1 at 60 pm (the shortest
wavelength plotted). the optically thin approximation is justified.

10.3.2 Centrally Heated Dust Cloud

In a dark cloud, the dust grains are heated by diffuse starlight from the outside. If
the dust c10ud contains stars inside. the dust grains are heated by the absorption of
direct starlight from within. For grains in an ionized nebula. radiative heating can be
in the forms of direct starlight. Lyn photons. and nebular continuum photons. In cases
where central heating sources are present, the dust temperature is not expected 10 be
uniform throughout the nebula. For dust grains at distance r from the star, the heaIinB
rate (1") is
m

I" = ] K,(4rrJ.,) dv. (10-25)

D
 10.3 Dust Emission 313

[00.0 = I I :
E L1689B E

10.0 E E

a: E 3
E : 3
IO E- E
E I E
_I .1
OJ I l l I I l I II I I I I I l I II I
10.0 [00.0 1000.0
Wavelength (urn)

Figure 10.5
The SED of the protostellar core of the dark cloud LIGBQB based on IRAS. ISO. millimeter.
and submillimeter photometry (from Ward-Thompson er al‘. 2002. MNRAS. 329. 251). The
entire spectrum is due to dust emission. Also plotted is a modified blackbody of 13 K using
eq. [0.24.

where 1,, is the mean intensity at the location of the grains. Assuming that direct
starlight is the dominant heating source. the mean intensity at radial distance r is
given by

Ju=4—I f B.(T_)da;
71'

1 ll R./r
= — dd 1 Bv(T,)sin9d9
47f D o

= ButzT.) [_ ms 013'”. (10.26)

where T. and R, are the tempelature and radius of the central star. respectively. At
great distances from the star where R, / r << 1. the mean intensity decreases as the
inverse squared of distance:

2
J, =1 (£5) BU(T.). (10.27)
4 r
314 Interstellar Grains: Physical Princesses

In the absence of thennal coupling between the dust and the gas. a dust grain
cools primarily by self-radiation. The cooling rate (A) by dust emission is

on
A z}; 4vadv. (10-28)

Substituting eqs. 10.? and 10.22 into eqs. 10.25 and [0.28 and balancing heating and
cooling. we have an expression that determines the equilibrium temperamrc of the
dust.

W1 R. 2 2 W 2

[3 3(7 <9.na)a.(r.)dv=fo (Qmmmau. (10.29)

Most stars radiate primarily in the visible pans of the Spectrum. Assummg
micron-size grains. most of the photons entitled by the central star have wavelengths
smaller than the grain size and Qm ~ 1. In this case, Q can be taken out of the integral
on the left side of eq. 10.29. giving

1 R. 1 ch_4
2(7) T =1; °° stutrdm, (10.30)

where a is the Stephan—Boltzmann constant. Substituting eq. I0. l5 into eq. 10.30.
we have

4 a 2
‘“ =— —— "_ ——+a.) flo) Te:4 ( 5:)
— (lil r I (10.31)
Tdi’) 6090 ]“(4 +a) §(4

where l" and 4' are the Gamma and Riemann zeta functions, respectively. The dust
temperature therefore decreases as a power law (Fa/(“'5 with increasing radius.
For a dust cloud with a central star of temperature 3000 K. the dust temperature is
600Katr/R.= IOO fora =1. Qo=0.l, audio = lum.
For a grain that emits like a blackbody. a = 0 and Q0 = 1. Since l"(4) = 6 and
{(4) = 11'" x90. eq. IOJI becomes

TN) = fl?—"'T_
2r . ( 10.32)

The dust temperature therefore decreases as the inverse square root of distance. The
same expression can be derived from eq. 10.30 by setting the integral on the tigltl-hfl-I'ld
side to aTj/rr.
If we take into consideration the variation of dust temperature as a function of
radius. the emergent spectrum would represent a composite of modified blackbodJES.
 [0.3 Dust Emission 3IS

each radiating at temperature T4. The observed flux would then be

f4rrjvdV
F” = ——
4:t't'D2
2 R9...
=23ng f nd(r)Bv(Td(r))4rt’r2dr. (10.33)

where R... and Rom are. respectively. the inner and outer radii of the dust cloud.
From eq. [0.31, the temperature distribution can be written as Td = To(ro/r)2/(4+“).
Defining a dimensionless variable

x = fl (L)m, (10.34)

and assuming a power-law density distribution (nd or r‘") for the dust component.
we can write eq. 10.33 as

Fbotvafiv‘flJ-EHMn-[xlflFl—fl-rul d _ (10.35)
ex—l

Since the integral over x is just a number (except for minor frequency dependencies
in the integration limits). the spectral shape is given by
mid") 'G-I-u‘l
Fvor u+ (10.36)

over the central part of the flux disuibution. If we assume a = l. for example. the
spectral index is 2.5a —— 3.5. For an optically thin cloud, the dust density distribution
can be inferred from the spectrum.
Figure l0.6 shows the optically thin dust spectrum of at = l and three different
density distributions. The turnovers at the short and long wavelengths are due to the
maximum and minimum dust temper-alum corresponding to dust at the inner and
outer edges. For a unifonn-density cloud (rt = 0). there is more dust in the outer
regions. The spectrum is dominated by emission by these cool dust particles. and
therefore peaks at long wavelengths. For the n = 2 case. which corresponds to an
equal amount of dust at each Td, the contribution to the total flux decreases with
increasing radius as the cooler dust emits less flux than warmer dust. Consequently.
the outer parts of the cloud have little effect on the spectrum.
Although the dust component is generally optically thin in the infrared. it can
be optically thick in the visible wavelengths. If this is the case, then the dust at the
outer parts of the envelope will see a deereasing amount of direct starlight. and will
be heated more and more by infrared photons emitted by nearby grains. As a result.
the dust temperature disuibution can no longer be expressed by a similar formula as
in the optically thin case (eq. 10.31). and the emergent flux has to be calculated by a
complete self-consistent radiation transfer model.
3l6 Interstellar Grains: Physical Processes

103 l— 1 _l_ I _l l_l l I 1 AL |_

[0° 2 sass-ism: 2 34:51:16:

Wavelength (pm)

Figure 10.6
The optically thin dust emission spectrum for a = l and three different density dishibutions
(n = 0. uniform density; nd at r' I; and n = 2. inverse squared). The central parts of the spectra
are well approximated by the power law of eq. 10.36.

One of the most commonly used l-D dust continuum radiation transfer models
is the DUSTCD code by C. M. Leung. Starting with an assumed optical depth To, the
program adopts an initial radiation field (Jv(r)) and calculates the dust temperauue
at every radius for a central star of luminosity I... temperature T... dust distribution
nd(r). and a dust opacity function xv. The derived dust temperature distribution Td(r)
is then used to calculate the new set of intensities 1,,(r) and the corresponding mean
intensity 11,0) used to calculate the heating term at every radius. These values are fed
back to the program for further iterations until convergence is achieved. The emergent
spectrum Fv(r = 0) is then obtained from the final I...
Figure 10.? shows the spectral energy distributions oftwo oxygen-rich AGB stars
fitted by DUSTCD. The upper panel corresponds to an optically thin case where the
reddened stellar photosphere can be directly observed in the optical and near infrared.
and dust emission appears as excesses at mid-infrared (A > 10 pm) wavelengths.
The emission features at 10 and 13 ,um are due to silicates (Section 11.2.1). The
lower panel corresponds to a dust envelope that is optically thick in the infrared. The
dust envelope completely obscm the central star. and the entire stellar spectrum IS
redistributed to dust emission in the infrared. The colder dust in the outer parts of
the envelope absorbs the emitted light from dust in the iruler regions. and the silicate
features go into self-absorption.
 10.3 Dust Emission 317

10,000 a ...... ...... . . . .

.f"‘~\ 20l94+3646 ‘
7 "~\ Blee
A IMF .r' °\ D0l8903 1
"in ‘ If IRC+40408
N l.“ \

E 100 r r; \ a
9
I)
. u'
to \.k .
B lo I' 1“ I

is
's .I
r \
l g I ". 1
. 5 \.\_ .
. ;.5 \.
0| - I - ...t 1 . . . I , 4...”: \

0.| I to 100
Wavelength (um)
10.000 ....m. ....W .
: 013044-621]
AFGL 230
... “mg fry-E... Gums—.02 '
L : .1 \ :
.. ' 1" \ i
5 10° = .w \ 1
d ' .r' .
Eb lo 5 § ‘3 1
:3-< F ‘1 3‘ .
‘4‘ l
-
r
.r
l
\_ . ‘.‘ g

l \ 5
l ‘1
0.1 one“. tumm. “is .
0.! 1 l0 IOU
Wavelength ( Jtlrt't)

Figure [0.7
The SED of mo oxygen-rich AGB stars fitted by radiative transfer models. The optical depths
at to urn are LS and 20 for the top and bottom panels. respectively. As the optical depth of
the envelope increases. the silicate features go from emission to absorption. and the stellar
continuum is entirely absorbed and reemitted in the infrared.

Figure [0.3 shows the SED of an extreme carbon star fitted by a 1-D dust
continuum transfer model assuming amorphous carbon grains. The model exactly
reproduces the transfer of energy from the optical to the infrared. The derived visual
extinction A v for this object is ~ 360 magnitudes. Such stars can only be seen in the
infrared and would never be discovered by Optical means.
318 Interstellar Grains: Physical Processes

lllllllll l i lllillI
--.._
IRAS 213l8+563|/ \
I
I
I
100 1'
f" I
'- I

E 2500 BBI
u ‘I
g ['0 |‘r

"g I“
{Eve i
'< l
I'
I
l
I
t
l
l :'
0_ I l4LttIIIf I 514l_ll|ll| I I II‘attil
0.1 1.0 10.0 100.0
Wavelength (pm)

Figure 10.3
The SED of the extreme carbon star IRAS 2l3l3+563| fitted by a dust continuum transfer
model. The dashed curve on the left represents the assumed photospheric spectrum ofa HOD-K
blackbody. The solid line is data from ISO SW3 and LWS. and the dotted line is the emergent
spectrum calculated from DUSTCD. The optical depth of the dust envelope is so high that the
photospheric output of the star is entirely transferred to the infrared

10.4 Themal Coupling between the Dust and Gas

For dust in ionized environments. there exists the possibility that dustcan be heated by
Lyar photons. Since the optical depth of the Lyu line is very high (> 10‘; see Section
5.1 l), a Lycr photon is absorbed and emitted many times by H atoms in the nebula
and therefore increases its chance of being absorbed by dust. Since recombination to
any state of H will end up in either the 223 or 22F states. the emission coefficient of
the Lya line is given by

. kw. (10.37)
J'Lytr: _:'1___fl'
"f".0 2 an— “225)

In an Ionized gaseous nebula of volume V, the luminosity of the Lyman tr line Is

LLyo' 2 4nija V

= Vh ”Lynne"? Z (1,, -a;25). (10.38)

In the two equations above. the sum begins at n = 2 for the first term InSlde the
brackets because recombination to the ground state will not produce a Lya photon. At
 10.5 Reflection and Scattering 319

low density, the 225' state will decay via the two-photon process. and decay from the
22.9 state will yield a Lyman a photon with a total power given by eq. l0.38. At high
density (n, > 10‘ cm"). the second term is dropped because atoms in the 225‘ state
can make collisional transitions to the 221’ state and therefore create a Lye: photon
(see Section 6.2). At Ta = 10“ K. the first term in the brackets has a value of 2.60 x
10‘” cm3 s'l and the second term has a value of 8.38 x 10'14 cm3 s‘ i. The emission
coefficients (41rj/ ramp) for Lya are therefore 4.3 and 2.9 x 10—24 erg cm3 5‘1 in the
high- and low-density limits. respectively.
Taking into account the contribution by Lyn: photons. we can rewrite eq. 10.29 as

it -- (Quito )B,(T,) dv+ —— =41! (val )B(Td)dv. (10.39)

r 0 ndV 0

The upper limit in the first integral now goes only to v] because all Lyman
continuum photons are assumed to be absorbed in the gas component in an ionization
bounded nebula and only Stellar photons longward of the Lyman limit are available
for dust absorption. The infrared excess (IRE) can be defined as the ratio of LII/LL“.
where LR is the total luminosity radiated by the dust component. Since the Lye: line
is difiicult to observe, IRE can be expressed in terms of the f—f flux. Dividing 41:11.3...
by eq. 6.21 and substituting into the definition of IRE. we have

quo-l' erg cur2 s")

IRE = A . 00.40)
Fson(mJY)
where the coefficient A has the value of ID and 1.5 at high and low densities,
respectively.

10.5 Reflection and Scattering

In our discussion on dust heating in Section l0.3. we assumed that all the incident
starlight is absorbed by the grain. In many circumstances however. only a fraction
of the incident light is absorbed. and the rest is scattered. For example. the visual
brightness of most solar system objects (planets. asteroids. comets. Kuiper Belt
objects. etc.) is due to reflected (scattered) sunlight. For an albedo w. the total flux
reflected from an object of size a at a distance r from the Sun as observed from the
Earth at a distance D is

F- =
m L°l 2( w i
(41w2 rra 4WD2
. .
('04!)
Since only (1 — w) of the incident energy is absorbed, eq. 10.30 has to be modified
to give an equilibrium temperature Td that is lower than the corresponding value if
there is no scattering:

1 R 2 at“1 m
- (-4) (l — w) “ =f Q.B.,(T..) dv. (10.42)
4 r If 0
320 Interstellar Grains: Physical Processes

In the_ mid and far infrared, all the observed llurt would be from self- omission, and
the mid-infrared spectrum of the object is

F _ 47ra2QuButTr)
"_ 41r D2 ' 00.43)
with the total infrared flux given by

Fm : f Fudv. (10.44)
If sufficient measurements in the visible and infrared can be made such that the
SED is well determined, then the ratio of the total visible (reflected) and infrared
(emitted) fluxes can be used to determine the value of the albedo:

fve
Fun E __"’_
1— m. (10.45)

Substituting the value of to into eq. lO.4l. the size of the object can be derived from
its observed visual brightness.
For a macroscopic object such as an asteroid. or = 0 and Q, is dependent on
the chemical composition of the solid. Assuming that it radiates like a blackbody
((2,, = I). an asteroid with an albedo of 0.2 at a distance of 2 AD. will have a
temperature of 186 K. If it has the shape of a sphere with a radius of 100 km. the
amount of flux emitted at l0 um would be 7.8 .ly if it is at a distance of I AM. from
Earth.
From eq. "14]. we see that the visual brightness of outer solar system objects
(r ~ D) decreases as r 4. Since Td falls off approximately as r ""2, the infrared
flux, which is proportional to D‘sz, also falls off approximately as r 4. Therefore
our ability to search for outer system objects through either reflection or emission
decreases rapidly with distance.

10.6 Dust Absorption in the X-Ray Region

Atoms in solid-state materials can absorb high-energy photons through electronic
transitions of inner-shell electrons. The typical energies to excite K- or L-shell elec-
trons of common elements range from 0. l- l0 keV in the soft X-ray range. Through
absorption spectroscopy against a bright X-ray continuum source. it is therefore pos-
sible to detect atoms (e.g.. O) in interstellar grains along the line of sight. However. in
order to separate the contributions between atoms and grains to the X-ray absorption.
it is necessary to have separate measurements of the gas column density (eg, by UV
spectroscopy) of the same element. Given enough sensitivity and spectral resolution.
it may become possible in the future to determine the crystalline structure of solid
particles by X-ray absorption spectroscopy.
 IO. 7 Stochastic Heating 321

10.7 Stochastic Heating

The preceding analysis of balance between heating and self-cooling assumes that the
energy absorbed by the grain from a photon is distributed efficiently throughout the
grain. However, for a grain of small size. the energy of a single photon is significant
compared to the intemal heat energy due to lattice vibrations. When a photon is
absorbed. the grain temperature may rise sharply to a high value before it drops back
to a low value until another photon hits. In other words, the grain temperature is not
a constant but fluctuates with time (Fig. 10.9). Since the rate of radiation varies as
T}. a small grain can radiate a lot while it is hot. A small grain can therefore radiate
at much shorter wavelengths than a classical grain in thermal equilibrium. This is
known as stochastic hearing or transient heating and is invoked to explain the high
color temperature of dust in the diffuse ISM.

8U
E
E
3.
E
2
C
E
O

2 2.5 3
Time (days)

Figure 10.9
A simulation of the effect of transient heating when a very small grain is exposed to a dilute
radiation field. The grain is assumed to have a minimum temperature of LS K as a result of
heating from gas collision and radiative heating from the cosmic background radiation. The
dashed line represents the averaged temperature (figure from K. Volk).
322 Interstellar Grains: Physical Processes

10.8 Interstellar Polarization

Scattering by a dust grain causes the reflected light to be polarired. Th: Multan:
electric vector is perpendicular to the line between the dust grain and the illuminating
star. if the dust is distributed in a spherically symmetric envelope, the POIEI'iution
pattern should be perfectly circular and the integrated polarization is zero. In an atti-
symmeuic dust envelope. as in a protostar environment where a disk-command Wind
has cleared away the dust inherited from the previous infall phase. or in the cm.
stellar environment of a post-AGE star where the mass loss process is enhanced in the
equatorial directions, the resulting polarization pattern should show a corresponding
axial symmetry. Figure 10.10 shows the polarization pattern in the reflection nehu.
losity around the protoplartetary nebula IRAS WHO-3224.

L'@”©'"°""'“
l" ~ 1

2‘ ':::::‘ -

. O _

iio- 1
hozl
h _ .

-2—3 _t

4LI I I ll'b I l I I I I i I l _‘

—2 0 2
rt_ofiset(“]

FigurelDJO
The distribution of the polarization vectors in the reflection nebula around IRAS [7150-3214
as observed by HST MCMOS (from Su et al. 2003. AJ', 126, 843).
 10. [0 Grain Processing 323

Since scattering is more efficient when the electric field is oriented along the
short axis of a grain. such differential extinction at optical wavelengths results in
linearly polarized starlight. If interstellar grains are not spherical and are not oriented
randomly. then starlight will show a residual polarization after traveling a certain
distance in the ISM. Stars that suffer from more extinction (i.e.. with larger values of
EU! — V)) are expected to show larger degrees of polarization. The typical observed
degree of polarization in the visible is 3% for a star at a distance of 1 kpc.
The detection of the polarization of starlight therefore suggests that dust grains
in the diffuse ISM are nonspherical and aligned. Since the alignment mechanism is
widely believed to be due to the galactic magnetic field, the observations of interstellar
polarimtion can therefore be used as a tracer of the galactic magnetic field.

10.9 Photoelectric Effect

The absorption of an ultraviolet photon by a grain will create energetic electrons that
diffuse in the grain. For a small enough grain. these electrons may reach the surface,
overcome the surface work function. and be injected into the gas phase, therefore
heating the gas (Section [4.8). Since grains also capture free electrons from the gas.
the net heating of the gas is related to the difference between ejection and capture
rates. This process will also apply to large molecules (e.g.. PAH; see Section 8.5), if
the ionization potential of the molecules is lower titan the Lyman limit.
The efficiency of the photoelectric effect will be reduced if the grains are charged,
because the electrons have to overcome the additional Coulomb potential in order to
escape. A typical photoelectric yield is 10%. After overcoming the surface potential.
the kinetic energy of the ejected electron is of the order of 1 eV. Since a difiuse UV
photon has energy exceeding 10 eV. the combination of yield and energy conversion
implies that only a few percent of the photon energy is convened to gas kinetic en-
ergy through the photoelectric effect. However, in environments where other heating
mechanism are absent (e.g.. in the diffuse ISM). photoelectric heating can be the
dominant source of heating of the gas.

10.10 Grain Processing

Once formed. grains are subject to further processing through growth. erosion. sput-
tering. and coagulation. The process of grain formation and growth is very poorly
understood. Although dust opacities are often calculated assuming spherical grains
(Section 10.2), actual grains in the circumstellar or interstellar environments are most
likely formed by stochastic growth processes leading to grains of irregular shapes.
For example, grain growth can proceed randomly by adding one basic unit at a time
(known as particle—particle aggregation). or grain growth can start with an ensemble
of N units that procud to form at random an ensemble of N[2 two-unit clusters.
which in turn form an ensemble of N[4 four-unit clusters. and so on. Results of a
simulation using these processes are shown in Figure 10.! l.
324 Interstellar Grains: Physical Processes

Figure 10.1]
Nonspherical dust grains generated by two stochastic growth processes using 514 units:
particle—particle aggregation (left) and cluster—cluster aggregation (Fogel and hung 1993_
rip}. 501, I75).

As grains are ejected as pan of the stellar wind. grain-gas collisions can lead
to sputtering. which in turn limits their growth to a large size. During the jaume,
through the ISM. grains can suffer from further destruction through collisions with
high-energy particles, or in the passage of supernova shocks (Chapter 16). Since
shocked gas has high temperatures (> 105 K, Section 16.2), the kinetic energy of the
gas can overcome the lattiCe potential and remove atoms from the grains by random
collisions. More interesting is the possibility that grains may undergo phase transitions
in a shock, with an amorphous grain changing into a crystalline structure (Section
11.3). For example, crystalline silicates are Seen in planetary nebulae but not their
progenitor AGB stars (Section 1 1.2); could this transformation be induced by shocks
in planetary nebulae (Section 16.4)?
On the other hand. mantles or surface coatings may deveIOp with the accretion
of gas-phase molecules when interstellar grains enter a molecular cloud. Chemical
reactions on the surface of grains are another avenue for the synthesis of molecular
species (Section 14.8). These mantles can be subjected to evaporation (sublimation)
when exposed to starlight. The chemical structure of the mantles can also change. in
panicular when irradiated with ultraviolet light (Section 13.4).
There are a variety of physical and chemical processes possible during grain-
photon. grain—gas. and grain—grain interactions, about most of which we have limited
empirical information and theoretical knowledge. Theoretical calculations in the
literature have suggested the destructive mechanisms in the ISM are very efficient.
and all grains produced by Stars should have been totally destroyed in the ISM. and
yet direct evidence of stardust can be found in solar system objects like meteorites
and interplanetary dust particles (Section 13.5.4). Clearly, stardust is hardier than we
think.

Further Reading

van de Hulsl. H. c. 1957. Light Scattering by Small Particles, Dover. New York-
 Eremises 325

Exercises

I. A dark cloud with a mean atomic weight (n) of 1.3 has a H density of to3 cut-3 and a
diameter of 2 pc. Assuming a dust—to-gas ratio of 3 x 10". a grain radius of 0.] nm.
a grain density of l gm cm 3. and Q = 2(A/AV) "5. calculate the extinction (A) at
the B, V. l. J. H. and K bands.
. Derive an expression for the wavelength corresponding to the peak of the emission
spectrum for a dust grain with emissivity Q or Jt " for different temperatures. Com-
pare this expression to Wien‘s law for blackbodies.
. A uniform-density dust cloud is heated by a central star of luminosity 3000 L0 and
a temperature of 3000 K. The grains have a uniform radius ofa = 0.1 pm. a density
of I g cm". an emission coefficient in the infrared given by

j” = mien umr'ndattm. (510.1)

and an absorption cross section to the stellar photons given by the geometric cross
section. if the gas mass of the cloud is 0.] Me. the dust-to-gas ratio is 10'], and the
dust cloud has inner and outer radii of 5 and 104 stellar radii, resPectively,

- calculate the temperature distribution of the dust (Td) as a function of distance

from the star.
- plot the total optical depth of the cloud due to dust absorption between I and
100 um.
- calculate and plot the dust emission spectrum (log AF; vs log A) between I and
[00 pm) if the cloud is located at a distance of 1 kpc.

. From eqs. 10.45, 10.43. and l0.44. show that for a grain that acts like a blackbody,
the sum of Fm and FIR is equal to (it?!) 1m2 (51?!) .
in
The Chemical Composition of
Interstellar and
Circumstellar Grains

Ever since interstellar dust has been recognized as the agent of extinction, there has
been along history of attempts to identify its chemical composition. The first hypoth-
esis was that it consists of “interstellar meteors." made up of iron orother metals based
on the analogy with meteorites. Later. possibilities of dielectric and icy grains were
investigated. Graphite and diamonds were also suggested as candidates. The debates
on the composition of grains are based entirely on photometric measurements and
the shape of the extinction curve (Fig. 10.2). Even with the introduction of polariza-
tion measurements and albedos determined from scattering, significant ambiguities
remain in the identification of the carrier of grains. The first quantitative clue came as
a result of the discovery of the 2175-5 bump in the extinction curve based on ultra-
violet observations from space. This feature was attributed to graphite. although its
true origin is not certain even to this date (Section 12.2).
The idea that dust can condense in the atmospheres of stars began with the
observation of irregular light curves of R CrB. whose sharp minima can be due to the
condensation of dusr. The recovery from minima could be the result of the ejection
of these grains from the star. From thermodynamical considerations. the most likely
candidates for such condensation would be refractory oxides and carbides It was not
until we acquired the capability of infrared spectroscopy in the late l9605 that the
chemical composition of stardust can be directly tested.
In Chapter 10 we discussed the heating and cooling of interstellar grains. assum-
ing a simple power-law absorption coefficient. However. like macroscopic objects
in our everyday surroundings. interstellar grains have colors that reflect their chemi-
cal composition. Specifically. the atoms within the grains can undergo electmnic and
Vibrational transitions and can have definite spectroscopic signatures. Spectroscopic
observations. if talten with sufficient spectral resolution and covering a wide enough
spectral region, should allow us to determine the chemical composition of the grains.
Micron-size dust particles, each made up of millions of atoms. are widely ob-
served in the ISM. How did these grains condense from atoms in the gas phase? Where
were they first formed? Did they undergo physical or chemical changes during their

327
328 The Chemical Composition of Interstellar and Circumstellar Grains

voyage through the ISM? Why are only certain kinds of solid materials made? Since
comets. meteorites. asteroids. the terrestrial planets. and Earth are just larger aggre-
gates of solid material. are these solar system objects chemically related to inlfl'stellar
grains'? The Understanding of the chemical and physical origins of interstellar stains
is. therefore. of great importance.

11.1 Optical Properties of Solids

Although atOms have specific and precise energy levels. when they are brought
together to form a solid. the energy levels spread out to form a hand because of u”,
Pauli exclusion principle. Given the large number of atoms in solids. the energy levels
within each band can be considered to be continuous. Every solid contains electmns
that are capable of conducting electricity. Whether a solid is classified as an insulator,
semiconductor. or metal depends on its band strucmre. 1f the valence electrons exactly
fill one or more bands, the solid is an insulator. Alkali metals (e.g.. Na). which have
one valence electron, must be metals. Since the width of the energy band increases a
the distanCes between atoms decrease. some of the bands will overlap in a crystal,
allowing electrons in a filled band to migrate to an unfilled band. This makes it
possible for alkaline earth elements (e.g.. Mg. which normally fills the 35 state) to
be metals. Bands that have more energy levels than electrons are called conduction
bands. whereas bands that provide electrons for conduction bands are called valence
bands. For transition metals, the d subshell is u5ually unfilled and they are therefore
naturally conductors. In addition, the energy levels of the d band usually overlap with
higher 3 and p bands. allowing elecu'on migration to occur.
If the band gaps between the valence and conduction bands are small. the solid is
an insulator at low temperatures but becomes conductive at high temperatures. These
are known as inuinsic semiconductors. When impurities are present in crystals. new
energy levels are introduced and can make an insulator a Semiconductor.
If we use the criteria above. then carbon. which has an electron configuration
152 252 2 p2 and an unfilled p subshell. should be a metal. However. in the diamond
crystal, which has ahigh degree of symmeuy. the 2 p level is separated into two energy
bands. with the 2p electrons filling the lower one. The large energy gap between the
lower and the upper 2p states makes diamond an insulator. The corresponding band
gaps in graphite are smaller. making graphite a better conductor.

11.1.1 UV and Visible Absorption

As in atomic and molecular transitions. the absorption of UV and visible light by a
solid is due to changes in 1he electronic structure. Electrons in crystals are an'angfi
in energy bands separated by band gaps where no electronic states exist. The size of
the band gaps determines the optical properties of crystals. For an ideal crystallinedr-
electric material. there is an energy gap between the valence band and the conduction
band. resulting in the material being transparent in the visible. Although arrwrlahotJs
materials can have electronic states in this gap. the transition probabilities of these
 I [.2 Inorganic Compounds 329

states are still low. This is demonstrated by the transparency of glass. an amorphous
material.
A solid with a large band gap (e.g.. diamond) will be transparent because no
electronic transition can occur across the gap. For a crystal to have a strong color.
its band gap has to be between 1.7 and 3.5 e‘V. corresponding to wavelengths in the
visible range. A band gap of ~ 2.5 eV will cause most of the blue light to be absorbed.
making the crystal a yellow-orange color. Many crystals. although transparent when
pure, can have bright colors if impurities are present. For example. ruby (red) and
sapphire (blue) are due to the presence of Cr“+ and Al+++ in Al203 (colorless).
respectively (see Section 11.2.3). Many of the transition elements have electronic
transitions in the visible. and their presence can bring colors to a crystal even though
the crystal itself has no band gap in the visible region.
The color of a solid is an important factor in the formation of solids in the
astrophysical environment. A material that absorbs poorly in the visible (transparent)
but absorbs strongly (and therefore emits strongly as well) in the infrared will suffer
from an inverse greenhouse effect. Since most of the heating radiation (primarily
from stars) is in the form of visible light. a material that can cool effectively by
radiating in the infrared has a better chance to have equilibrium temperatures drop
below condensation temperatures, therefore allowing it to condense into solids.

11.1.2 Infrared Absorption

Absorption features in the infrared are generally due to vibrational transitions in
the grain lattice. In the solid phase. rotational motions are no: possible. and the
vibrational—rotational transitions seen in gas-phase molecular spectra are replaced by
a broad. continuous band at the vibrational frequencies. In a crystalline solid, lattice
vibrations create plane waves, which are referred to as phononr. Due to the symmetry
of the structure. only a few of the possible lattice vibrational modes are optically
active. Therefore. crystalline solids have only a few sharp features in the infrared.
Since amorphous solids have a lower degree of symmetry. most modes are
optically active. The variation of bond lengths and angles also means that there is
a wider range of vibratiOnal frequencies. leading to broader features.

11.2 Inorganic Compounds

Inorganic chemical processes often lead to the formation of homogeneous solids with
a definite chemical structure and highly ordered atomic arrangements. In the natural
environment, these compounds are called minerals. Minerals are classified by both
their chemical composition (oxides, sulfides, etc.) and their structure. If the lattice
structure is highly ordered, the solid is referred to as in a crystalline state. Specifically.
interatomic distances (bond lengths) and bond angles in a crystal are always the same
and the structure has translational symmetry. If the atoms are arranged more or less
randomly in a disordered manner. the solid state is referred to asamorphous. Although
the bond lengths in amorphous solids are nearly the same. the bond angles can have
large variations.
330 The Chemical Composition oflnterstellrtr and Circumstallar Grains

Crystalline structures are formed when a liquid has sufficient time during the
cooling process to arrange itself in an ordered structure. If the cooling is rapid
the disordered state is preserved in the freezing process. resulting in an mm“;
structure. A direct condensatiOn to solid from the gas phase. as in the case of grain
formation in a stellar atmosphere. often results in an amorphous structure (Section
13.1).

11.2.1 Amorphous Silicates

The first astronomical identification of the vibrational modes of solids was the 91
um feature attributed to the Si—O stretch of amorphous silicates. This feature was
detected in emission in the circumstellar envelopes of late-type stars as well as in
absorption in molecular clouds and H II regions by ground-based obsenrations in
the late 19605. In the IRAS all-sky survey, the silicate feature was detected in over
4000 O—rich stars by the Low Resolution Spectrometer (LRS). An accompanying fea.
ture at 18 pm is identified with the Si——O—-Si bending mode of silicates (Fig. [1.1),
The wide and smooth profiles of the 9.7- and lfl-um features indicate the absence
of long-range order typical of crystalline minerals. and the substance is therefore
likely to be amorphous in nature. One example of an amorphous solid is silicate
glass. which is made up of basic units consisting of a silicon atom in the center
of an oxygen tetrahedron, linked together by sharing oxygen atoms in the form of
Si—O—Si bonds. The variation of the Si—O—Si bond angles results in the disor-
dered amorphous structure. This linked su-ucture can be broken with the inuoduction
of positive ions such as Mg.
The shapes and peak wavelengths of these two features vary in different objects.
For example. the 93'th feature is found to be broader (FWHM ~ 4.3 pm) and at
longer wavelengths (10.6 run) in the Taurus dark cloud than in the Orion Trapezium
region. Amorphous melilite (CazAIZSiO-fi is also known to have broad features at to.
15. 19. and 34 pm. but they have not been unambiguously identified.
Astronomical silicates are found to be more absorptive in the near infrared than
their terrestn'al counterparts. suggesting a higher value of the imaginary part of the
refractive index (k, Section 10.2). This could be due to the presence of impurities
such as iron or iron oxides. as they are known to affect the optical properties of
silicate glasses from the UV to the near infrared, resulting in astronomical silicates
sometimes being referred to as "dirty silicates." The emission profiles of the 9.7-
and lS-um features of astronomical silicates are well determined from the IRAS LRS
observations. These profiles give us empirical absorption coefficients that can be used
to derive the optical constants of astronomical silicates.

11.2.2 Crystalline Sillcates

Silicates are the most abundant group of minerals in the Earth's crust. Most of the
terrestrial silicates are in crystalline form. which has a basic tetrahedral structure.
Four Of2 ions occupy the four comers of the tetrahedron with the Si4+ ion located
in the center. The four surplus negative (— I) charges of the 0 atoms are bonded With
Si" in the center of other tetrahedra.
Crystalline silicates can be in the fortn of olivines or pyroxenes.01ivines have the
general chemical formula Mg2_z,Fe;,SiO4, where 0 5 x 5 1. Although having d'f'
 I [.2 Inorganic Compounds 331

IRAS LRS
I I I I I I I I T I I I I I I I I I I

6.0 _

TA 50 L - " —
(um - ' .3. TXCam ‘
E 4.0 — .' a. _
u .' '. .
g 30 r_ .r' 3'1. '\ —
"s . - '~. -. -
E: 20 _- : \‘Q..'h u""l'"'"n. -

1.0 — "" AFGL 5357 “a“ j

00 l I I I I I I I I I I I | I I I I I

8 l0 [2 [4 16 13 20 22 24
Wavelength (”I“)

I I l I ‘I— t I I I t—l r I I I
2.0 l 'J— I

5 1.6 - ' .0... -

all” _ ‘ .P -.. AFGL 2.59 L”... .- _

5 1-2 '_ We :: I 0.... . 1... _-

En _ 'n .. : 'nl- ..

e
a
03 —— '-a. 3 :-
Hum-- ._ e-,.“.".~-.._n.,o__. __

e o" :' AFGL 230

°"‘ ‘ '25/ —
0 0 I I l I I I I I I I I I I I I I I I I

'6 BlOI21416l8 20 22 24
Wavelength (pm)

Figure 11.1
IRAS Low Resolution Spectra showing the 9.7- and Ill-um silicate features in emission (top)
and in absorption (bettern).

ferent chemical compositions. these crystals have identical crystal structures (known
as isomorphism). The Mg and Fe ions in the crystal can substitute for each other
at random in varying proportions. The two ends of the series M32804 (1 = O) and
Fe28i04 (x = l) have common names of forsteritc and fayallte. respectively. Other
metals. such as Mn. Co. and Zn. can also replace Mg and Fe in the olivine structure.
Pyroxenes have the general chemical formula of MgquexSiOg. The two ex-
tremes MgSiOJ (x = 0) and FeSiO, (x = 1) are called enstat'ite and ferrosilite, respec-
tively. Enstatite is an important constituent of the upper mantle of the Earth. Natural
silicate minerals often contain other impurities such as sulfides and oxides of Fe. Cr.
332 The Chemical Composition ofInterstellar and Circumsteiiar Grains

and T1. The olivine group of minerals has an orthorhombic structure consisting of
SiO.. tetrahedra linked by (Mg, Fe) atoms. each of which has six 0 neighbol-s.
In addition to Mg—Fe pyroxenes, calcium and sodium pyroxenes are also mible
An example of calcium pyroxene is diopside (CaMgSizofi). which has a lame;
structure similar to enstatite with half of the Mg atoms replaced by Ca, Sodium cm
combine with Al. Fe. or Cr. forming jadeite (NaAISizog). aegirine (NaFeHSizofl)
and kosmochlor (NaCrSiZOS). respectively. '
A rich structure of nan-ow emission bands due to crystalline silicates was discov-
ered by the ISO mission. Pure enstatite has strong features at 9.9, 10.7. 11.1. 11.6,
18.2. 19.3. 40.3. and 43.3 urn. whereas forsten'lc has strong features at 10.0. 11.2,
16.3, 23.5. 27.5. and 33.5 um. Figure 11.2 shows a comparison of the 150 spam
of IRAS 10215-5916 with the laboratory spectra of synthetic forsterite and ensuring,
The matching of a number of these features suggests that the material is magnesium
M.A.C. "‘ B( 100 K)

_1
.l

..
_l

.1
Trllllllllllllllll'

1.0

IIIIIJIIIIIIIII‘
0.3
0.6
0.4
0.2

i-
Illllllllllflllllllll

Illlllllllllllllll
200

150
Flux [Jyl

100

50 III]
-4-
M.A.C. * 3(100 K)

.1

I .0
I Illllllllllllllllll

0.8
0.6
0.4
0.2 Enstatite
I I i_ J. I I I 1 l I L i 1
20 30 40
it [um]
Figure 11.2
The continuum-subtracted ISO spectrum of IRAS [0215- 5916 compared to the normalized ab-
sorption coefficients of magnesium-rich crystalline silicates forsterite and cnstatite muluplled
by B_.(l00 K) (from lager et at. 1998.A&A. 339. 904).
 ”.2 Inorganic Compounds 333

l015 : I I I r I r I I l I I I

: I996 September/October UT
_ “=23 AU

10"" r

'E
U
I
E _.
u:‘ -
m
10-" .— —_

_ U
__ J 1

.5 I Ill/i I I I I I I l I I I
lO' 1 10
Wavelength (pm)

Figure!”
The spectrum of the comet Hale- Bopp on October [996 showing Ihe presence of both
amorphous (broad feature at 10 um) and crystalline silicates. The light solid line between
7 and 40 pm is from ISO SWS. The dark solid line is a synthetic model fit to the SED. The
long-dashed line is a 5770K blackbody curve representing the reflected solar spectrum (from
Harker er al. 2002. ApJ. 500. 579).

rich (I z 0). Crystalline silicates have been found in young stars. evolved stars. and
comets (Fig. [1.3). The weakness of these features suggests that the abundance of
crystalline silicates is small in comparison to amorphous silicates.

11.2.3 Refractory Oxides

Refractory oxides are of panicular interest because they are expected to be the first
condensates in the atmospheres of O-rich stars. From equilibrium studies. the first
condensates in a cooling gas of cosmic abundances are compounds of aluminum.
titanium, and zirconium (Section 13.1). Since Al and Ti have relatively high abun-
dances. their oxides could be the seeds of circumstellar grains. Theoretical studies of
the condensation of refractory oxides have been made in the context of the early solar
system. envelopes of AGB stars. and supernova shells. Examples of some cornm0n
refractory oxide minerals are discussed below.
334 The Chemical Composition oflnrersreflar and Circumsteflar Grain:

0 Corundum: a-A1203 is known as corundum in its naturally occurring fm It is

the hardest known natural substance after diamond. In a pure state. it is colorms
But when a small amount (~ I in 5000) of the aluminum atoms are replaced it);
chromium atoms. it takes on a reddish color and is commonly known a; ruby
When the impurities are iron and titanium, it has various shades of blue am“;
known as sapphire.
Aluminum oxides have also been made in an artificial form with cubic gym.
metry (y-Alzog). This transforms to an amorphous form at higher tcmpetarums_
The changing spectral behavior of these transitions is shown in Figure 11.4.

I_I—I"_I'I[llilllrllvi

i 1773

fl
t |273

1073
'
t
Transmittanee (a.u.)
'

-..| 3 _
“I
.

n
I

l
I

03
I__.-

83
I_a_l_n
‘l’

IILIIIIIIIIIIIIJI|IIJ¥LA

10 500 tooo 1500 2000

Wavenumber (cm‘ 1)

Figure 11.4
Infrared transmission spectra of A1203 at six difierent temperatures (labelled in units of dew
Kelvin). The two lower temperature curves correspond to y-Al103. the middle two curve: to
amorphous A1203. and the two upper curves to a-A1203 (from Begemartn er al. 1997. AP]-
416. 199).
 11.2 Inorganic Compounds 335

10.- l | l —
0.01 -
3.1

u: I I
g 0.6 _- .2.

'i 2
£0.4- -
Z I .
- d

0.2 n

0.0
Jir
12 13 I4 15 16 n
llflml
Flgure 11.5
The rtcn'malized profiles of the lit-pm feature averaged over the ISO SWS spectra of ll M
stars. The sharp features at 13.48. 13.37. 14.97. 15.40. and 16.18 am are due to vibrational
rotational transitions of gas-phase C02 (Section 8.1) (adapted from Posch er a1. 1999. AM.
352. 609).

A possible reaction for the condensation of corundum from the gas phase is

A120 + 21110 —> A1203 + 211;. (11.1)

A broad feature centered around 13 um was first discovered by the IRAS

LRS. This feature was first suggested to be due to corurtdum. which has a
feature at 12.7 urn. Altemative suggestions include glass (amorphous Si02. with
an emission peak at 12.3 urn). spinel (12.95 pm). and rutile (13.4 pm). From
the mean residual ISO spectra of stars showing the lB-um feature. the peak
wavelength is found to be 13.0 nm with a FWI-M of 0.6 pm (Fig. 11.5). A
companion feature at 16.8 out may also be present.
' MgA1104: Magnesium aluminum oxide MgA1204 is the most common mineral
in the spinel group. which has a general composition form of A3204. with A
being Mg. Fe. Zn. Mn. or Ni. and B being A1. Cr. or Fe. At. high pressures.
olivines transform into spinels. which have a denser structure.
0 Iron oxides: Metallic iron can easily be oxidized in an environment rich in 02.
Hematite (a-Fezog) is the most common form of iron ore. This hard and heavy
oxide mineral has a variety of forms. including red (othenvise known as rust) and
steel grey. Wustite (Fcl J,0) is a terrestrial mineral of iron monoxide. FeO can
336 The Chemical Composition of Interstellar and Cirrrrmsteflar Grains

form easily on the surface of iron grains. and has been postulated as a Possible
ingredient of interstellar grains as early as the 19705. It has also been suggww
as a possible carrier of the broad emission feature at ~ 20 um observed in Grid,
stars. An emission feature at 19.5 urn observed by ISO has been attributed to a
mixture of Mg—Fe oxides (e.g., Mgu .FeolgO).
° Rutile: The most common and abundant terrestrial form of titanium oxide (T102)
is rutile. Each Ti ion is surrounded by six 0 ions at the comers of an OCHhedron
- Periclase: Periclase (MgO) has a cubic structure similar to that of halite (NaCj),
with Mg and 0 ions occupying the comers. In a natural mineral. Fe. Zn. and Mn
may substitute some of the Mg atoms. Other members of this group are Wustite
(FeO), lime (CaO). bunsenite (N i0). manganosite (MnO). and so forth. MgO has
a resonance feature at ~ 15 um. but has not been detected astronomically.
° Calcium oxides: A number of calcium oxides. including hibonite (CWIIOWL
grossite (CaAI407). CaA1104, and CaAluOn, have been identified in meteor-lugs.
Analysis of the isotopic ratios of the hibonite grains in meteorites has shown
some of them to be of pro-solar origin. probably formed in the outflows of O-tich
stars. In a circumstellar environment, hibonite is expected to form by reaction of
corundum with gas-phase Ca. Laboratory studies of hibonite have found spectral
features at 12.3. 15.9, 21.1. 25.1. 34.4, and 78.7 rim, although no detection has
yet been obtained in stellar sources.

Although refractory oxides are not as widely observed in the astrophysical envi-
ronment as silicates, they have been found in the form of pre-solat grains in meteorites.
A large number of corundum. as well as some spinel and hibonite. particles have been
detecred in the acid residues of meteorites (Section 13.5.4).

11.2.4 Silicon Carbide

ln carbon stars. where the photospheric abundance of C exceeds 0. all 0 atoms are
tied up in CO and the surplus C atoms can form various C-based molecules and
grains. The formation of silicon carbide (SiC) grains in outflows from AGB stars was
predicted based on theromodynamical equilibrium calculations (Fig. 13.1). The I 1.3-
,ttm feature. due to the stretch mode of the Si—C bond of SiC. was first detected by
ground-based infrared telescopes in the 19705, and later detected by IRAS LRS in 700
carbon stars. making it the most common solid-state feature in C-rich circumstcllar
envelopes (Fig. l 1.6). Unlike amorphous silicates. there is no Spectroscopic evidence
for the presence of SiC grains in the diffuse ISM as of 2005.
SiC is a covalent compound with two major crystalline forms: or-SiC. which has
a hexagonal or rhornbohedn'c structure and has a feature peaking at 11.4 um: and
,B-SiC. which has a cubic structure and has a feature peaking at [1.0 pm. Based on
comparison between laboratory and astronomical data. a-SiC is believed to be the
prevalent form in carbon stars. HOWever, all pro-solar SiC grains found in meteorites
are of the 5 type (Section 13.5.4). Recent laboratory measurements have suggested
 ”.2 Inorganic Compounds 337

1500

M300 ‘nergcmzs ')

1000

Wavelength (,urn)

Figure 11.6
50 SWS spectrum of V 03 showing the l 1.3-,um SiC emission feature.

that the astronomical spectra can in fact be better fitted by fi-SiC. If this is indeed the
case, then there is no discrepancy between astronomical and meteoritic SiC.
The wide presence of SiC in carbon stars suggests the possibility of the presence
of metal carbides. involving, for example. titanium (Ti). vanadium (V). zirconium
(Zr), and other transition metals. These metal carbides have high thermal and me-
chanical Stability, which makes them possible candidates as condensates in stellar
outflows. Unlike SiC. these transition metal carbides show metal properties and have
high reflectivity in the visible and infrared regions.

11.2.5 Carbonats
The carbonate ion (CO; ’) has a u'igonal structure with a carbon atom centrally
located in a triangle of O atoms. The carbonate ion can combine with Ca. Na. Fe,
Al. Mn, Zn. Cu, and other rare-earth elements to form a variety of carbonates.
For example. carbonates such as calcites (CaC03). dolomite (CaMg (C092). and
aragonite (CaCOJ) are the major constituents of limestones. which make up the bulk
of the nonterrigenous sedimentary rocks and represent ~ 2% of the Earth's crust.
Some of the magnesium atoms in dolomite can be replaced by iron, the ex-
treme met of which is ankerite (CaFe(C03)2). Another isostructural member of
the dolomite group is kntnahorite (CaMn(C03)2). Both dolomite and anken'te have
338 The Chemical Composition aflnrersrellar and Circumsrellar Grains

emission features at 62 um. whereas calcite has a feature around 90 #m. Magne-
site (MgC03) and siden'te (FeC03) have no strong far-infrared bands and would be
difficult to detect.

11.2.6 Ices
In addition to the crystalline form of ice that we are familiar with in everyday life.
ice can also be in an amorphous form. Amorphous ice has varying 0—H bond angles
and has a structure similar to that of arnorphOUS silicates.
Although the ice form of H20 in the ISM was long anticipated. it turns out that it
is not as abundant as the more robust materials such as silicates. The 0—H stretching
mode at 3.0 pm and the bending mode at 6.0 out are detected in the spectra of prom
stars. The ice form of another common molecule C0 is characterized by its C-—-0
stretch band at 4.67 am. Other molecular ice forms that could be present in the ISM
include N2. HCN, Czi-lz. 03. and so on. Also possibly present in small quantifies an:
organic species like nitriles. ketones. and eSters. Some of the commonly obsenred
solid-state features in the ISM are given in Table 11.1.
Figure 11.7 shows the infrared spectrum of NGC 7538. In addition to the absorp
tion features of silicates at 10 and IS pm. a number of ice features (H20 at 3.0 and
6.0 pm. CO at 4.7 pm. CO; at 15.3 um. and CH4 at 7.7 am) can be seen. The ob-
served broad absorption feature ato nm is due to the H—O—H bending mode of H20.
with possible conu-ibution from the C—0 stretching mode of formic acid (HCOOH).
The broad feature centered at 4.62 pm (labelled ‘XCN' in Fig. ll.7) is seen in a
number of young stellar objects. but not in the diffuse ISM. Its position is indicative
of a stretching mode of nitriles (compounds containing the —CEN group). hence the
name 'XCN’. Other possibilities include ketenes (compounds containing the C=C=O
functional group). which have absorption bands in the range of 4.5-4.3 urn. Simple
cyanate salts have strong C—N stretching bands in the range of 4.5-4.62 um, and Ihe
cyanate ion OCN‘. which forms by ultraviolet or ion irradiation of ices (Section I14)
containing H20. C0. and NH3. is a strong candidate as the carrier of the 4.62-urn
feature.
Heavy water (HDO) ice has a feature at 4.07 pm. which has not yet been detected.
The current upper limit for the HDOIHZO ice ratio is < 0.0024101.
The absorption profiles of ice features can be affected by the composition of the
host matrix and its thermal history. For example. the solid CO absorption feantre
can be shown to be resolved into two overlapping components: a broad, shallow
component at 4.632 urn due to C0 in a matrix of H20. and a narrow component
at 4.673 um due to pure C0. C0 mixed with C02. N2. or 02. or CO mixed with a
small amount of H20. With a high (R ~ 25.000) infrared spectrometer available on
ground-based telescopes. the CO ice profile can be analyzed in detail. For example.
the C0 ice profile in Figure 11.8 can be fitted by a mixture of pure CO ice at 10 K.
H20:C0 = 4:1 at 50 K. N2:02:C02:CO = 1:5:0.5:l at 10 K.
Although energetic processing of ices containing ammonia can give rise to
complex organic molecules (Section 13.4). unfortunately signatures of NH; i065 are
hard to detect as almost all the strong bands of NH; ice overlap with bank of water
and silicates.
 [1.2 Inorganic Compound: 339

Table 11.1
Molecular vibrational bands in solids

Molecule Mum) Mode

H20 3.05 0—H su'etch

6.0 H+H bend
13.3 Liberation
NH; 2.96 14—11 stretch
9.35 Umbrella
CH4 3.32 C—l-l stretch
7.69 C—H defamation
CO 4.67 C—O stretch
C01 4.27 C—O stretch
15.3 O—C—O bend
CHJOH 3.08 0—H stretch
3.35 C—H stretch
3.53 (2—11 stretch
6.39 0—H bend. C—H deformation
9.75 C—O stretch
MgSiO, 9.7 Si—O suetch
19.0 0—Si—O bend
Mgfiio. 10.0 Si—-—O stretch
19.5 0—Si—0 bend
mm, 9.5 Si—O stretch
20.0 CFSi—O bend
FeISiO. 9.8 Si—O stretch
20.0 Hi—O bend
SiC 11.2 Si—C stretch

Front Whither. D.B.C. I992. Dust in the Galacrr‘c Envtmnmt.

Institute of Physics.

The solid-state vibrations of C02 appear near the same frequencies as in the
gas phase because the molecules are held together by weak forces and the molecular
structure is largely unchanged in the solid state. It has four transitions in the mid
infrared; the strongest is the asymmetric stretching mode (uj) at 4.27 pm. Figure l 1.9
shows spectra of the bending mode ( oz) at 15.2 urn. The two combination modes ( u, +
v, and 21:; + v3) at 2.697 and 2.173 pm. respectively. are weaker (see Chapter 8).
340 The Chemical Composition of Interstellar and Cimumstellar Grains

103 5
H20 c|-|I (H20)
(HCOOH) t i
10’ ; (XCN) \
A ' ”CO: C02 Silicate
3' .

:I
E.

10"

NGC 75381RS9
[0‘l .
"3'
Hum)

l0’ I;
' l3co2 \
Silicate
3"' IO‘ .r
c0; -
E“ E CHJOH

I0" _ H20 -
\CHJOH was).
3 5 IO' 20
Wavelength (urn)

Figure 11.7
150 SW5 spectra of the protests: NGC 7538 11189 (lop panel. from Whinet er al. 1996. AM.
315. L351) and W33A (bottom panel. from Gibb et al. 2000. ApJ, 516. 347). The two broad
absorption features are due to H10 ice (3.05 pm) and amorphous silicates (9.? put)- “I:
feature labelled as XCN could be due to OCN'.

Provided that the ice absorption features are optically thin, the ice abundances
can be determined by dividing the integrated optical depth of the features by the
band strengths measured in the laboratory. In dense clouds. the abundance of H20 ice
relative to H is z 10“, which is a significant fraction of the total 0 abundance.
The observations of ice features in young stellar objects open the pcvssilil'lfit)r
of studying the physical and chemical processes that lead to their fonnation. These
include accretion of gas-phase species. grain-surface reactioas (Section 14.8). and
 R14 R13 R12 R11 R10 119 113 117 :

th 5°“ ‘30 we M..r“""i-: _

g“ 0'0 :1“ 35% (WNW “EM ““
M”:k“ ,1fr ' I W 1I. “Z:
.6 0'5 :[— i'
E Ei 1 ‘
g 1-0?” R43 R3! “2| '1' R0 Pl 172 P31 P43 PE»l ‘.
| _.
I.S "
2160 2150 2140 213.0
Wavenumber (cm")

Figure 11.8
Keck NIRSPEC spectrum of the young stellar object L148? in the Taums molecular cloud
showing both Ihe solid ice and gas-phase C0. The broad absorption feature 4.67 pm is due to
C0 ice. whereas the narrow features an: fundamental band vibmtjonaI—rotalional transitions
of C0 in the gas phase (Section 7 .5). Positions marked by the '+' signs are transitions of ”CO
(from Boogert er al. 2002. Astmphys. 1., 568. 761).

I'II‘IIII'VIII'lIII'IIUI IllllrvltIIIIIIIIIIIIl—r1

SgrA' gas = '16 fit: It! 0 W3 IRSS gas = 25 fit = “6

.---—&—.

GL2136gas=17 fit=ll7 NGC75381RSIgas=25 fit==116

Nonmlized optical depth

W33A gas = 23 fit = 116 NGC 7538 IRS? gas = 26 fit = 114

1:..1iii.ltli.lnii_i_th|. IllllllllllllljJ—Llllnlll
14 14.5 15 15.5 l6 14.5 15 15.5 16 16.5
Wavelength (pm)

Figure “.9
ISO SW5 spectra (dots with error bars] showing the C02 ice bending mode at 15.2 um. Solid
lines are fits based on laboratory data for an ice mixture 011-120. CHJOI-I. CO; at different
temperatures (from Geralu'nes er a1. l99'9. ApJ, 522, 357).
342 The Chemical Composition of Interstellar and Circumstellar Groin:

irradiation by energetic photons or particles (Section 13.4). The eVaporation of ices

into the gas phase can also alter the circumstellar chemistry. leading to the for-mafia“
ofcomplex species such as dimethyl ether (CH30CH3). methyl formate @1130ch
vinyl cyanide (CHICHCN). and ethyl cyanide (CHJCHZCN). The interplay man
gas-phase and grain-surface chemistry is therefore a new area of astrDchernisn-y that
needs further exploration.

11.2.7 Luminescence
The general term luminesczrtce refers to the phenomenon of the emission of Visible
photons after the absorption of energy in matter. The initial input can be in the form
of radiative. kinetic. chemical. or heat energies. In the terrestrial environment, many
minerals fluoresce under illumination by UV light of particle collision. In the [SM
probably the only relevant process is photolumineseence. where a solid-state material
emits visible light when irradiated by UV light. Photolumineseenee occurs when a
photon of energy greater than the band gap is absorbed by a semiconductor. leading to
the creation of an electron—hole pair. These pairs quickly tltenttalize to the limits ofthe
conduction and valence hands. When they recombine. they emit a photon of energy
close to that of the band gap (Fig. l 1.10). Metals do not undergo photoluminesma:
because there is no band gap.

L
A ‘—
Conduction band

W hum
Dere%_.wvu thL

Valence band

_ .__s ._._,
7" Nomadialive Radiative

Figure 11.10
A schematic diagram illustrating the mechanism of photoluminescenee. When a photm of
energy nu is absorbed by the material. it creates an electron—hole pair (hfl‘). Afler they
thermalize to the limits of the conduction and valence bands. this pair can either mm
nonradiatively through impurities and disorder sites in the crystal or dangling bonds on '50
surfwe. or radiatively through photoluminescenee (adapted from ledoux er al. 2001. AM.
377, 707).
 1' L3 Organic Compounds 3-43

Specifically. a photon of energy but is emitted with an efficiency of n by a wide

band gap material upon the absorption of a photon of energy hv. The remaining
energy stays in the material and is reemitted as infrared radiation. For an individual
solid particle. the ratio of the power emitted via luminescence to that emitted in the
infrared is
Plum = '7th

Put (1- WW + nUw - hvt)

= fl—. (11.2)
(hv — nhvr)
The luminescence efficiency 11 can therefore be estimated by observing this ratio.

11.3 Organic Compounds

Carbon (C) is the fourth most abundant element in the Universe after H, He. and O.
In the ISM. the total carbon abundance is estimated to be 225 :t: 50 atoms per 106
H atoms. In addition to its high abundance. C is also a versatile element capable of
forming a large variety of compounds. The carbon atom. with a ground-state electron
configuration of 1522s12p2. can have up to four atomic wavefunclions from the 25
and 2p electrons to form hybrid orbits for bonding (Section 7.3). The combination of
a and it bonds allows carbon atoms to be linked to neighboring atoms in three kinds
of sites (Figure 11.1 I):

- sp': acetylenic-type bonding (CHECH) where linear chains of atoms are linked
by alternate single 0' and triple (one a and two rr) bonds.
- spz: three a and one If bonds form a u-igonal geometry. One example is the
benzene-type bonding characteristic of an aromatic ring structure. Another ex-
ample is ethylene-type bonding (H2C=CH2).
- sp’: alkane-type (CzHfi) bonding where four a bonds form a tetrahedral geom-
euy. These are refen-ed to as aliphatic sites.

The family of organic commands that contain only H and C are called hydro-
carbons. The simplest family of hydrocarbons is known as alkanes. containing only
C—H and C—C single bonds. Since all four electrons of the C atom are paired with
the electron from an H atom. alkanes are also called saturated hydrocarbons. The first
member of this family is methane. which has one C atom and four H atoms (CH4).
The next in the series is ethane (CzHfi). and then propane (Cal-la). The general formula
of this family is Cnl'lz,1+2. Similarly. those hydrocarbons with C—C double bonds are
called alkenes. and those with C—C triple bonds are called alkynes. Alkanes. alkenes.
and alkynes are collectively referred to as aliphatics. in contrast to aromatics. which
have a carbon ring structure made up of spz sites.
344 The Chemical Composition ofInterstellar and Circumsrelfar Grains

Hybrid orbital

(C-site) SP‘
(acetylenic)
5P1
(aromatic.
5P’
(aliphatic)
straight olefinic} tetrahedral
plane. trigonal
Functionality
Aromatic
R H
\C C,

C/ \C R
\ / H U
/C_C\ l E
CH ’=‘ C —— H c E
/H C // \ C l-

C:C C
\
R
Olefinic

H H u
/
CH2
c=C\ /C\
1 s
5
H C / H 35)
Olefinic C
H
I U

CH3 (3 E
c // \H E
H

Figure 11.11
Example of different hybridizations of carbon (from Papoular er al. 1996, AM. 315. 222).

The C atom can combine with H. O. N. S. and so on to form a variety of groups.

Some examples are shown in Figure l [.12.

11.3.1 Crystalline Forms of Carbon

Crystals can develop into a variety of forms (called polymorphism) depending on the
environment. Diamond and graphite are the two most well-known fronts of crystalline
carbon. Although they are made up of the same element, they have very different phys-
ical characteristics. Diamond is hard. colorless. and transparent. whereas graphite is
soft. black. and opaque. These differences result from the crystalline structures. Di-
amond and graphite are both formed with large assemblies of C atoms with a sinslc
 I 1.3 Organic Compounds 345

\n
\
\ /

l
/
=C —-CEC— ——- -—
\ \\ //
Alltene Alkyne
/C—C\
Arene

_.|._.;_. ”Vi—r ”i ‘7‘—

Alcohol Ether Amine

:3: :3: :6:

'—'C—'—
u | l
——('l'—'C—'H
l u l
—(l:——C—(|L“—

Carbouyl Aldehyde Kelone

Figure 11.12
Examples of common functional groups in organic compounds. The bonds that are not labelled
are assumed to be attached to C or H atoms in lhe rest of the molecule.

type of site arranged perfectly (see Table l 1.2). Diamond is a covalent network solid
composed of sol-hybridized atoms in a three-dimensional lattice, whereas graphite
is a two-dimensional sheet of benzene-like rings with sp2 sites.
Because of its chemically robust nature. diamond has long been conjectured to
be a component of interstellar dust. However. this possibility was taken seriously
only when nanometer-sized diamonds grains [nanodiamondfl were extracted from
meteorites in 1937. The abundance of nanodiamonds in meteorites is about 1400
ppm. The isotopic anomalies (e.g., Xe) found in these grains are suggestive of their
pro-solar origin (Section 13.5.4). Possible mechanisms of the synthesis of diamond
in space include growth by chemical vapor deposition and grain grain collisions in
high-velocity stellar outflows. such as under supernovae conditions (Section 13.3).
Diamond is a semiconductor with band gaps at 7 and 5.45 eV. Since only
photons of energies greater than these values can raise electrons across these gaps.
diamond therefore absorbs strongly in the UV but poorly in the visible. Because of
its symmeu'ic structure. vibrational uansitions are largely forbidden and crystalline
346 The Chemical Composition ofInterstellar and Circunutellar Grains

Table 11.2
Solid carbon materials
___—‘-—-_

Material Structure Bonding state

1“-

Diamond Tetrahcdtally arranged C atoms in a cubic Four rp3-hybridiud otbitnls

structure

Graphite Layers of hexagonally arranged C atoms .sp1 in the layers

in a planar system

Fullcrite solids Geodesic structure of cageliltc sphernid Mixed hybridization State

Curbyne Long chains with either conjugated triple .rp hybridization

bonds or cumulated double bonds

Noncrystalline Planar graphitic microcrystallits Different spzjspJ mics;

material embedded between clusters mixed hybridization states
HAC Hydrogenated amorphous carbon spa. tr)3 > spl'

Table adapted from Henning and Salami 1995. Science. 282. 2204.

diamonds have an almost featureless spectrum. However. when inflated by H atoms.

CH bonds can form in the carbon surface and the vibrational modes of these bonds can
be observed in the infrared. In fact. surface groups dominate the infrared spectrum
of pro-solar nanodiamonds. Because of diamonds high UV absorption coeflicient.
small diamond grains can be heated up to ~ 1000 K in the vicinity of hot stars. At
such temperatures, the continuum peaks in the near infrared. and some of the surface
vibrational modes can be observable in emission. A number of C—H stretching and
bending modes. as well as C—C stretching modes. are expected in the 3—15 its:
range. Figure ”.13 shows the comparison of the infrared spectra of two Herbig
Ate/Be stars with the laboratory absorbence spectra of diamond nanocrystals prepared
using microwave plasma chemical vapor deposition. The two major features aredue to
C—H stretches of hydrides attached to the crystalline surface.
Diamond itself is transparent and colorless and its brillance and color when
exposed to light are mainly the result of its high index of refraction and dispersion.
With impurity and point defects. diamands also exhibit luminescence (Section 1 1.1.1)
under sunlight or UV radiation. Electronic transitions at defect centers can also cause
sharp lines called zero-phonon lines. The strength of these zero-phonon lines is
dependent on the impurity content and thermal history of the diamond. If detected.
these lines could be the most definitive way of confirming the presence of interstellar
diamonds.
Diamondoids are hydrocarbons that have a diamond-like carbon lattice with
the dangling carbon bonds terminated with H. The smallest diamondoid is ctofln
(adarnantane). The higher members. which have two, three. four. and five face-
fused cages. are called diamantane (CMHm). triarnantane (CmHu). terrains-"W
 ”.3 Organic Compounds 34'!

UM _ I 1— '— r 10

0.05

0.04 g
33
o 3‘
g a
s 0-03 .3
fi
'E
0.02 tn

0.0l

0.00 . _I_ |

2950 2900 2850 2300

Frequency (cm")

Figure [1.13
The infrared Spectra of Elias I (curve a) and HD 97048 (curve is) compared to the labomtory
absorption spectrum of O.l-ptm hydrogenated diamond nanocrystals (curve c) taken at 950
K. The 3.43- and 3.53-pm fearures are identified as C—H stretches on C(IOD) and CO I I)
surfaces (from Chen er al. 2032. J. Chem. Phys. 116, l21l).

(CnHu). and pentamantane. respectively (see Fig. ll.l4). While tetramantane has
four isomers of the same molecular weight, pentamantanes have nine isomers with
molecular weight 344 (C26H32) and one isomer with molecular weight 330 (Czsflao).
The higher diamondoitts (polymantanes) are more varied in molecular geometry and
structural complexity. Because of their structural stability, diamondoids are difficult
to synthesize and they are mostly isolated from petroleum.
The best-known example of a crystalline structure made of a mixture of sites
is firllerenes, which have a geodesic structure. For example. C60 contains 60 5p: hy-
bridized carbon atoms in 32 five— and six-membered rings in the shape of a soccer ball.
The curvature of C50 is induced by the presence of the five-membered rings. Because
fullerenes have no edges and therefore no dangling bonds. they are particularly sta-
ble. C60 was produced serendipitously in the laboratory as a result of laser irradiation
of graphite during a process trying to simulate the production of long-chain carbon
348 The Chemical Composition of Interstellar and Circumsrellar Grains

Figure 11.14
The front and side view of the diamondoid CHI-123 (from Chen er al. 2003. J. Chem. Phys,
119. 110626).

molecules such as cyanopolyynes in a circumstellar environment. Theoretical studies

suggest that fullerenes can be formed in space via the buildup of C1—-—Cm chains from
C+ insertion. ion—molecule reactions, and neutral—neutral reactions (Chapter l4), Be-
cause of the stability of its structure. C60 and related molecules are expected to be
widely present in the ISM. Extensive searches of C60 through its UV absorption band
at 3860 A have placed an abundance limit of < 0.01% of interstellar carbon in lhe
form of C50. Searches for the 3.6-,um feature in carbon stars have also been unsuc-
cessful. Laboratory work has suggested that C33 is very stable. however. searches of
the 7.1- and 7.5-rtrn vibrational bands of C63 have also yielded an upper limit of0.3%.
Polyhydrofullerenes (Cme. m = l. 2, . . . 60). also known asfidleranes. are the hy-
drides of fullerenes and represent a new class of hydrocarbons. This family may be
present in the ISM because of the stability of C60 and the abundance of H. Although
there is no definite detection of fullercnes in space, their existence is strengthened by
their presence in meteorites (including higher fullerenes; see Section [3.14).
It is interesting to note that fullerenes in the form ofconcentric shells are possible
and stable. This structure. known as carbon onions, can be made by electron beam
irradiation of carbon soot in a transmission electron microscoPe. or by heat treatment
and electron beam irradiation of nanodiamond. It has been suggested that carbon
onions could be responsible for the 2175-11 absorption feature in the diffuse ISM
(Section 12.2).
A fourth kind of crystalline carbon is polyyne. which consists of a long linv
ear chain of sp-hybn'dized carbon atoms with alternating single and triple bonds
(—CEC—CEC- - -CEC—-CEC—. etc.). An alternative form of carbon chain is
that of cumulenic bonding with successive nearly equivalent length double bonds
(:C=C=C...C=C=C:) (Section 8.4). They are collectively known as corbyne (Table
11.2). Polyynes have been suggested as the precursors in the formation of polycyclic
aromatic hydrocarbons (Section 8.5) and soor in combustion flames as well as inter-
mediates for the synthesis of fullerenes and carbon nanotubes.

11.3.2 Amorphous Forms of Carbon

Noncryslalline C is characterized by different 5;)2 [5,03 hybridization ratios as well 85
mixed hybridization states. In the interstellar environment. carbonaceous substances
 H .3 Organic Compounds 349

made up of all three types of sites in various concentrations are possible. Amorphous
carbon. in its pure form. is made up of a random network of spzlsp" bonds. Since
there is no one definite structure. the optical properties of amorphous carbon are
dependent on the relative number of various bond types and the physical conditions
under which they are made. The optical properties of the grain. such as the emissivity
in the far-infrared and submillimeter wavelengths (the spectral index a, Section 10.2).
are dependent not only on the internal structure but also on the morphology of the
grains. Calculations based on a continuous distribution of ellipsoids show lhat the
value of a can change significantly as a function of .rp2 content.
An example of amorphous carbOnaccous carbon in our everyday life is soot.
Soots are produced by combustion of hydrocarbon molecules in a flame and are
characterized by large defected aromatic rings with oxygen functional groups such
as phenols, alcohols. others, carbonyls. and so forth.
Examples of other amorphous carbon structures include hydrogenated amor-
phous carbon (HAC) and quenched carbonaceous composites (QCC). HAC consists
of islands of aromatic (spill bonded C atoms joined together with a variety of pe-
ripheral 5p? and 5p] bonded hydrocarbons (Fig. “.15). QCC are produced by the
technique of hydrocarbon plasma deposition where methane gas is heated to 3000 K
with a microwave generator. allowed to expand into a vacuum chamber. and con-
densed on a room-temperature substrate. The resultant dark. granular material is
shown by electron micrography to have an amorphous structure. Since QCC consists
of only H and C and the conditions under which it is synthesized resemble the cir—
cumstellar environment of AGB stars. it could have astrophysical significance. Mass
spectroscopy of QCC suggests that its aromatic component typically consists of one
to four rings, and most have only one to two rings. Infrared spectroscopy of QCC
reveals a mixture of Sp, sp2. and spa bonds. Upon heating. the strengths of the sp-2
features increase relative to the sp3 features, suggesting QCC can become graphitized
at high temperatures. Observed infrared spectra of circumstellar grains show broad
emission plateaus Characteristic of HAC and QCC (Fig. I |.l6).
Coai, formed from fossilized hydrocarbon materials, also contains a mixture of
sp. 5,02, and sit)3 bonds. Terrestrial coal is classified by its H and 0 content relative to
C. Coal is believed to have evolved naturally with time through heat and pressure,
changing from “low rank” to "high rank" through decreasing H and 0 contents.
Structurally. it increases its long-range order by stacking aromatic planes to form
randomly oriented basic structural units. eventually ending as graphite. Different
ranks of coal can be distinguished by their fluorescence propenies, with lower-
rank coals having higher visible fluorescence under UV light {Section ”2.7). In
the infrared. highly ranked coal can be distinguished from lower-ranked coal by its
infrared spectra (Fig. l l.17). The catagories of coal (in rank order from low to high)
are peat, lignite, bituminous, semi-anthracite, anthracite, and graphite. The urban
content changes from < 50% in peat to > 95% in graphite. Age is also considered
to be a factor in the transformation of coal from low to high rank. When coals of
different ages are buried to the same depths. the older coals have a higher rank.
Kerogen is a solid sedimentary, insoluble, organic material found in the upper
crust of the Earth. In contrast to coal. which is found in bulk rocks, kerogen is usually
found in sandlilte dispersed fomt. Structurally. kerogen can be represented by random
350 The Chemical Composition of Interstellar and Cin‘untsteilar Grains

Figure 11.15
Schematic diagram illustrating the types of C bonding in HAC: sp' (circled dots). Jpz (filled
circles). sp3 (circled crosses). and H (open circles). Double dots indicate bonding to other
atoms (from Jones et at. 1990. 9.1. R. Asrmn. Soc“ 3] . 567).

arrays of aromatic carbon sites, aliphatic chains (—CH2——),.). and linear chains of
benzenic rings with functional groups made up of H. O, N, and 8 attached (Fig. l [.18).
The O atoms can be in ester (—O—C=O). ether (C—-0—C). or hydroxyl (—OH)
groups.
Kerogens are classified into types I. II, and [Il according to their OIC and HIC
ratios. Type-l kerogen has a high initial WC and low initial OIC ratioI whereas type-[l1
kerogen has low initial HIC and high initial OIC ratios. The composition of type Ii is
in between that of types I and 1]]. At depths of 2-3.5 km. where the temperatures
are in the range of 70—100°C. cycloalkanes (CHI-[2") and alkanes (Cum-n+2) are
released from kerogens (in particular from types 1 and ii) and form the ingredients
of crude oil. At greater depths with temperatures > [50°C, methane (CH4) “Id
ethane (C2145) (the main components of dry natural gas) are released. In between the
releases of oil and dry gas are the “wet gases" made up of propane (C3113) and bum“
((341110)-
The fractions of H, S. N, and 0 relative to C in kerogen are similar to those
in lipids (fat and fatty acids). leading to the belief that kerogens are fanned as a
result of the decay of living organisms. Bacteria and other microbes are thought ‘0 be
responsible for this degradation. which occurred under an O—deficient environment
 :AJ._.L__L._L l ‘Ji-iqul . i...—
Arbitrary unils

1
4
r’
“\‘T/

HAC at 713 K
‘2‘ -¢ 1 1 47 ‘ . ‘1 |----

‘2 T

TE
"-1
x j
E
U
‘.
-

55 I l

.5. V854 Cen 1

4 e a .. 10 I {2 ' 14 ..
Wavelength (flm)

Figure 11.16
Comparison between Lhe ISO SWS Spectrum of the R Corona: Borealis star V854 Cen with
the laboratory specmun of HAC (Lambert at at. 200i. ApJ, 555, 925).

Semi-anthracite
Absorbame (Lu)

Wavelengm ( ,um)

Figure [1.11
The infrared absorption spectra of semi-anthracite and anthracite coals. Note the meme of
the 6.9-, 122-. and 13.3-mn features in semi-anthracite but not in anthracite (from Guillois er
at. 1996, AP], 464. 810).
352 The Chemical Composition ofInterstellar and Cr'rrumstellar Grains

Figure 11.l8
Schematic diagram illustrating the structure of kerogen of type II. he shaded areas are clusters
of benzenic rings and the broken lines are carbon chains. Cal-I bonds are not plotted (from
Papoular 200l . AM. 378. 597).

11.4 Summary

Astrochemistty at the beginning of the twenty-first century is in a similar stage of

development as astrophysics in the early 19005. There is an increasing body of spec-
troscOpic obServations. suggesting that there are minerals or chemical compounds
in space that are similar to those in the terrestrial environment. This has assured us
that the general principles of chemistry in our laboratory also apply in space. The
drastically different physical conditions in space, however, may also produce new
or unfamiliar materials. or known materials radiating under unusual conditions. The
discowry of a new form of carbOn, fullerenes, in the laboratory is the result of the
desire to reproduce the cyanopolyynes seen in the ISM. It is hoped that astronomi-
cal spectroscopy will motivate new directions in laboratory research. leading to an
expansion of frontiers in laboratory chemiSLry.

Further Reading
Bellamy. L. J. I976. 77:: Infrared Spectra ofCampl'ex Molecules, 3rd ed.. Chat-mm 5‘
Hall. London.
Whittet. D. B. C. 2003, Dust in rhe Galactic Envimnmem, 2nd ed.. Institute of Physics.
f1;
Carbonaceous Grains

Although the cosmic abundance of carbon is less titan that of H. He. and 0. it is the
most abundant condensable element. Its chemical versatility implies that it can easily
polymerize. When condensed from the gas phase, C-based molecules can form chains
and rings. 11 is therefore likely that interstellar grains have a major component that is
made up of C, or C-based backbone strucmre. In addition to the familiar carbon solids
based on .rp2 (graphite) and sp3 (diamond) hybridizaticns. there are other transitional
forms of C with a mixture of sp2 and sp3 hybridizations—amorphous carbon. soot.
and so on (Section 11.3.2). Although solids based on sp hybridization (polyyne and
cumulene) are fragile and difficult to make in the laboratory. their synthesis may be
much easier in the circumstellar or interstellar environment.
Advances in infrared spectroscopy. especially from space observations, have
made possible the identification of the chemical compositions of interstellar and
circumstellar grains. With increasing spectral resolution and sensitivity. an increasing
number of emission and absorption features have been observed. which could be
identified with vibrational modes arising from different molecular bonds in a solid.
From eq. 7.10. we can see that various chemical bonds have characteristic stretching
frequencies. which are dependent on the masses of the attached atoms. the strengths
of the chemical bonds. and hybridization (Section 11.3). For example. the bonds are
stronger in the order of sp > sp2 2» sp3. and the C—H stretching frequencies are
highest in an acetylenic bond (sp) (v0 ~ 3300 cm 'or~ 3.0 urn) than those in alkenes
(spz) (v0 ~ 3100 cm ' or 3.2 um). and in alkanes (sp3) (v0 ~ 2900 cm‘1 or 3.4 pm).
From laboratory infrared spectroscopy of molecular compounds. the characteris-
tic vibrational frequencies of various functional groups can be identified. Table 12.]
gives a list of vibrational frequencies of common functional groups. Since a solid
particle contains millions of atoms and many different sites. the exact frequencies of
any infrared bands will shift depending on the site from which the band arises. Of
particular interest for astronomy are carbonaceous grains. The high abundance and
chemical versatility of carbon make possible the creation of a rich variety of solid-
state compounds. In the 311m region where there exists an atmospheric wind0w and
ground-based spectroscopy is possible. there are a variety of vibrational modes that
potentially can be identified (Fig. 12.1). In the l0—um window. we also have access
to the C—H out of-plane bending modes. Most other vibrational modes have to be
observed from space.

353
354 Carbonaceous Grains

Table III
Infrared bands for representative functional groups

Functional group Molecular motion Wavenumher (cl-n") Wavelength (um)

Aliens C—H stretch 2950-2800 3.57—3.39

CH2 bend ~ 1455 ~ 6.83
CH3 bend ~ 1375 ~ 7.27
CH1 bend (4 or more) ~ 120 ~ 13.89
Alberta =CH su-etch 3 100-3010 3.32—3.23
C=C sh'etch (isolated) 16904630 6.l3-5.92
C=C stretch (conjugated) 1640-1610 6.2l—6.10
C—H in—pllnc bend ”SO-12% 7.75—6.99
C—H bend (monostlbstitutod) ~9908t~910 ~10.IO&~10.99
C—H bend (disubw'tuted - E) ~ 970 ~ 10.31
C—H bend (disubstituted - 1.1] ~ 890 ~ 11.24
C——H bend (disuhstltuled - 2.) ~ 700 ~ 14.29
C-—H bend (ttisubstituted) ~ 815 ~ 12.27
Alkym acetylenic C—H suetch ~ 3300 ~ 3.03
C.C triple bond suetch ~ 2150 "-4.65
ACCtylcnic C—H bend 650—603 16.67-15.38
Aromatics C-—-H stretch 3020-3000 3.33—3.3I
C=C stretch -- l600 dt ~1415 ~ 6.25 0'. ~ 6.18
C-—H bend (mo) 770-730 & 715-685 13.70-12.99 & 14.60—13.99
C—H bend (ortho) 170-735 13.6l-12.99
C—Hbcnd(meta) ~880&~780&~690 ~11.36&~12.82&~l4.49
C—H bend (para) 850-3“) 12.50-l I .76
Alcohols 0—H stretch ~ 3650 at 3400—3300 ~ 2.14 or 3.03-2.94
C——0 stretch 1260-1000 "1.00-7.94
Ethets C—O—C stretch (dialkyl) [300-1000 10.00-11.69
C—O—C stretch (diml) ~ 1250 & ~ 1 I20 ~ 8.00 & ~8.93
Aldehydes C—H aldehyde stretch ~ 2850 & ~ 2750 ~ 3.5] a ~ 3.64
C=O Stretch ~ 1725 ~ 5.80
Ketones C=0 stretch ~ 1715 ~ 5.83
C—C sketch 1300-1100 9.09—7.69
Carbonylic acids O-—H stretch 3400—24-11) 4. 17—194
C-O suetch 17304700 5.83—5.78
 Carbomceou: Grains 355

Talk 11-1

W;
Maul group Molecular malion Wavcnurnbcr tern") Wavelength (um)
_________.___
C-—O stretch 1320-1210 3.26-1.53
0—H bend 1440—14“) 7.14—6.94

Ester! C=O Stretch 1750—1135 5.76-5.71

C—C(O}—-C stretch (acetates) 1260-1230 3.13—7.94

C—C(O)—C stretch (all others) 1210—] 160 3.62—3.26

Aciddllflid‘s C=O stretch 1310-1775 5.63—5.52
C—Cl stretch 730—550 18.13—13.70
mm C=0 stretch 1830—1300 0'. 1775—1740 556-146 & 5.75-5.63
C—O stretch 1300-900 1 LI 1—169
Aminfi N—H stretch (I per N—H bond) 3500—33“) 3.03-2.86
14- H bend 1640-1500 6.67—6.10
C—N stretch (alkyl) 1200—1025 9.76—8.33
C-N stretch (Iryl) [MIEO BID-7.35
N—H band (00p) ~ 800 - 12.50
mugs N—-H stretch 35111—3180 3.14-2.86
C=O stretch 1680-1630 6.13—5.95
N—H bend 1640—1550 6.45—6. 10
N—H bend (to) 1570-1515 6.60-6.37
Nitriles C,N triple bond strctch ~ 2750 ~ 4.4.4
meymates —N£=0 struch ~ 2210 ~ 4.41
minus —N=C=S stretch ~ 2125 ~ 4.71
Imim R2C=N—R struch 1690—1640 6.10—5.92
Niu'ogroups —NO; (aliphatic) 1600-1530& 1390-1300 6.54-6.25 & 1.69—7.19
NO; (aromatic) 1550—1490 & 1355—1315 6.71—6.45 & 7.60—7.38
Hermann S—I-I stretch ~ 2550 ~ 3.92
Sulfuxides 5:0 smelch ~ 1050 "- 9.52

Stflfoncs S=0 stretch ~ 1300 & ~ 1150 ~ 7.69 & ~ 3.70

Sullomlcs S=0 stretch ~ 1350 & ~ 11750 ~ 7.41 0'. ~ 0.85
8—0 stretch 1000—750 1133—10“)
Wm P-- H stretch 2320—2270 4.41—4.31
PHhend 1090-810 1235—9.”
”(whine Oliks P=O 1210—1140 8.77-3.26

Whmubkby new
356 Carbonaceau: Grains

H—X stretching frequencies

v. cm 1
3600 3400 3200 3000 2300 26“)
I— l _I. I l _I_ I I I l 1 I
I I I I I I I I —[ I
2a 3o 3.2 3.4 3.6 3'3
1. Mm

—C_

0—H stretch

Free Complexed

H10 I' .
Alcohols Cal-boxy Ic ands

CH30H o\ 0—H
CHJ—{CHgn—OH \ C/
I
Figure 12.1
Characteristic vibrational frequencies ofN—H. 0—H. and C—H stretches in the 3-urn lesion
(adapted from Pendleton and Allarnandola 2002. ApJ’S, 138‘ 75).
 12.! The Aromatic Infrared Band: 357

While atomic and molecular emission lines have narrow intrinsic line widths
and their observed line widths are the consequence of Doppler broadening. emission
features from solid-state materials show broader intrinsic widths and they are referred
to as emission bands. The widths of the observed features therefore provide a hint that
these features originate from a solid rather than from a molecular species.

12.1 The Aromatic Infrared Bands

A family of strong infrared emission bands at 3.3. 6.2. 7.7. 8.6. l1.3, and 12.7 out
was first detected by the KAO in the young carbon-rich planetary nebula NGC 7027
and is now widely observed in H II regions. reflection nebulae. planetary nebulae.
protoplanetary nebulae, and the diffuse [SM of our own and other galaxies (Figs. 12.2,
12.3). Solar system objects. such as carbonaceous meteorites. interplanetary dust
particles. and Manian rocks. are also known to display these features. The energy
emitted in these bands can be a significant fraction of the total dust continuum energy
output of galaxies. and the identification of the carriers of these features is therefore
important for the understanding of the ISM and galaxies.

Orion

300
1Pi(10'“ergcm 2 s ')

2 4 6 B 10 l2 l4 l6
Wavelength (pm)

Figure [2.2
The infrared spectrum of evolved H II regions such as the Orion bar is dominated by the
aromatic emission features at 3.3. 6.2. 7.7. 8.6. and 11.3 urn. The narrow lines (not marked)
in this [30 SW5 spectrum are emission lines from the ionized region.
353 Carbonaceour Grains

24“) I *l I i I 7* r i I I I
_ fiT——:——-—.
Aromatic bands in the Red Rectangle .
2200 F ._

2000 — _‘
. C—C stretch

3. 130° T c=c stretch '

5 IGOO F c.“ _
n ' C-H out-of- lane bend
a” 1400 — in-plane bend P :1
.5: . s
3" 12‘” C—H stretch ‘
"* [000L J
300 — :1
i- u:

600 - _
400 r 4 . t . L g I . L . I . l
2 4 6 B IO 12 I4 16
Wavelength (urn)

Figure 12.3
The Red Rectangle (HD 44l'l9) is a reflection nebula with a BB-AO central star. Its ISO
spectrum (SWSOI and SWSO6) is dominated by the MB features and a strong continuum.
Because of the low temperature of the central star, there are no atomic emission lines in the
spectrum.

While they are usually observed in emission, the 3.3- and 6.2-um features have
also been seen in absorption in the diffuse ISM and molecular clouds. These prominent
features are often situated on tap of broad emission plateaus. Infrared imaging of
H II regions and planetary nebulae with filters centered on these emission features
shows that the band emission regions are concentrated in a narrow zone between
the ionization and photodissociation zones. Observations of niece features far away
from exciting sources show that the underlying continuum can be very weak. with the
3.3mm feature to continuum ratio being as high as 30.
The fact that the strengths of these infrared emission features correlate with the
C10 ratio of planetary nebulae suggests a carbon—based carrier. Comparison with
laboratory infrared spectroscopy of organic compOunds has led to the identification
that these features arise from stretching and bending modes of various C—H and
C——C bonds in aromatic hydrocarbons. For this reason. that: strong infrared emission
features are now known as aromatic infrared bands (AIBs). Possible carriers of
these AlBs include PAH molecules (Section 8.5) and HAC. QCC grains. or coal
(Section 11.3.2). ISOCAMobservatiOns of reflection nebulae show that the strengths
of the A135 are independent of the central star temperature (Fig. 12.4). “53‘5““
that the AIBs can be effectively excited by visible photons. This. together with the
invariance of the feature profiles (peak wavelengths. FWHM. etc.) from source 10
 [2.1' The Aromatic Infrared Band: 359

LB
U!
III-[imiv

‘l

d
.

Illlll'l_l_[‘l_I_lIIIlll

114111]IlillllillllllwlLlllllll
"'3 ”(NGC 1333)
vdasgmoczoes)
5-"
o vdB 133
in
M
E"
D
i, (sealed)
& II1—rlttlllvrllll
.0
o
.9
UI b 5

I-
m

3
E

Z
Wavelength (pm)

Figure 12.4
ISOCAM CVF spectra of three reflection nebulae showing the 6.2-. 7.7-. 8.6-, l [.3-. and 12.7-
,um MB features. Each spectrum has been divided by its respective IRAS l2—um broadband
flux to show that the features have similar peait wavelengths. spectral shapes. and continuum
levels independent of the temperatures of the illuminating stats (from Uchida et at. 2030. ApJ'.
530. 317).

source, suggests that the carrier is more likely to be a solid than a mixture of small
molecules.
Although the chemical symbol of the simplest aromatic molecule. benzene
(C6116). is written as having altemate single and double bonds between the C atoms.
the electrons are in fact symmetrically distributed and all bonds are equivalent. How-
ever. if H atoms or other side groups are attached to the comers, orthe ring is attached
to one or more other carbon rings. this symmetry is broken and the bonds are no longer
equivalent. The stretching of the C—C bonds gives rise to emission features at 6.2
and 7.7 pm. Although the 6.2— and 7.71am features are often attributed to the specific
stretching of the C=C and C—C bonds. respectively. this distinction is not appropri-
ate for aromatic molecules as the bonds are essentially equivalent. Instead the 6.2-
and "LT-urn features represent two of the strongest normal modes. In a large PAH
molecule or graphite, the 7.7mm feature is a superposition of a number of motions,
each with slightly different frequencies. This interpretation is consistent with astro-
nomical observations where the 6.2- and 8.6-,um features are relatively well defined.
the ”LT-um feature is composed of at least two subfeatures (at 7.6 and 7.3 um). and
possibly more (Fig. 12.5).
360 Carbonaceaus Grains

Wavenumber (cm ')

1600 1400 [2“)

Flux density (Jy)

I
1.—

i Orion bar D5

o 1 4L

6 7 8 9
Wavelength (pm)

Figure l2.5
11te ISO SWS spectra of the reflection nebula NGC 7023 and the H II region Orion bar show
that the 7.7-,um AIB feature is made up of two components at 7.6 and 7.8 um. and possibly
also a shoulder feature at 7.4 urn (from Peelers er al'. 2002. AM. 390. 1039}.

The stretching of the bond between the C atoms on the ring and the adjacent H
atom gives rise to the strong feature at 3.3 um. This band corresponds to the stretching
mode when an H atom is attached to a nonsaturated C. as in an aromatic or alkene
molecule.
in a saturated hydrocarbon (alkane). the C——H stretch occurs at longer wave-
lengths and the CH vibrations can be in a symmetric or asymmetric mode. For a
methyl (—CH3) group, the symmetric mode corresponds to a vibration in which all
three H atoms are stretching in phase, whereas the asymmetric modes compond l0
one bond contracting while the other two are extending or vice versa (see Fig. 12-6)-
In general. the asymmetric modes are stronger than the symmetric mode.
In the I l—lZ um region. infrared emission is dominated by C—H out-OFF]?-11c
bending vibrations of the aromatic units. A list of the commonly observed [R emissron
features and their identifications is given in Table 12.2.
 12.! The Aromatic Infrared Bands 361

H H H H
xxc/ \/
Figure 12.6
Illustrations of the asynunettic (left) and symmeu-ic (right) stretching vibrations of methyl and
methylene groups.

The exact frequencies of the out-of-plane bending modes are strongly dependent
on the number of neighboring CH units on each ring. For a large aromatic unit. most
of the rings will be attached to other rings. and there will be few isolated CH groups.
When a CH group has no adjacent CH group. it is referred to as a solo-CH (see
diagram 4 in Fig. 12.7). When there are two adjacent CH groups on a ring, it is
referred to as duo-CH (diagram bin Fig. 12.7). and so on. Since these peripheral C—H
bonds are not equivalent, they have different bending frequencies. This allows the

Table 12.2
Hydrocarbon infrared emission bands
observed in the ISM

A (um) Mode

Aromatic (Sp!)

3.29 IC—H stretch (v = l —> u = 0)

6.2 C=C su'etch

1.6—8.0 C—C stretch

8.7 =C—H in-plane bend
11.2 nC—H out-of—plane bend for
nonadjacent. peripheral H atoms

Aliphatic (sp’)

3.38 Asymmetric CH3 Stretch

3.42 Asymmetric CH: stretch
3.49 Symmetric CH3 stretch
3.51 Symmetric CH; stretch
3.46 —CH stretch
6.85 CH0}, asymmetric deformation
7.25 CH0.” symmetlic deformation
362 Carbonaceous Grains

(a) (b)
H H

a ._ 3" . H

./ "'

H H '
H H

H H

H H
(C) (d) (e)

Figure 12.7
A schematic diagram illustrating the possible number of CH groups in aromatic molecules. A
Cl-l group with no neighboring CH group is called a "solo" group (diagram 0). one neighboring
CH group is called "duo" (diagram 12). and so on (from Hudgins and Allamandola 1999. ApJ.
516. L41).

peripheral structure of the aromatic units to be determined from infrared spectroscopic

observations. Far example. the infrared spectrum of semi-anthracite shows distinct
features at 11.5. 12.1. and 13.3 pm. which can be identified as arising from 5010-.
duoitrio-. and quarto-CH. respectively. For small unit PAHs. the solo-CH modes are
in the 11.1—11.6 um range. duo-CH in the 11.6—12.5 urn range. trio-CH in the 12.4-
13.3 urn range. and quarto-CH in the 13—116 urn range.
From the observed relative strengths of the 11.7-. 12.1-. l2.4-. and 13.3—un1
features. it is possible to estimate the relative numbers of solo, duo. trio. and quartet
functional groups and the possible structures involved. For example. solo groups
imply a long straight molecular edge. duos and trios correspond to corners of the
structure. and quartets are due to rings attached to the structure (Fig. 12.3).

12.1.1 Side Groups

When a group of atoms join together in a specific spatial structure and take part
in chemical reactions as a single unit, they are refined to as radicals in inorganic
compounds or side groups in organic compounds. Examples of inorganic radicals
include ammonium (NH4), carbonate (C03). cyanide (CN). hydroxide (0H). silicate
($0, or Si04). and so forth. Examples in organic groups are methyl (CH3) and
ethyl (Csz) groups. which are derived from methane (CH...) and ethane (C2116)-
respeetively. .
Since the interstellar environment contains elements in addition to C and H. fl
is natural to expect that the carbonaceous dust in the ISM contains impurities such
 12.} The Amnmric Infrared Band: 363

Structure 4. "5H”; Sid = 4.0; sit = L] '. slq = 3.0

Figure 12.8
Examples of molecular structures having difl'ertnt ratios of solo (5). duo (d). trio (0. and quartet
(q) modes. 1116 numbers inside the rings indicate the number of adjacent CH groups per ring
(fmrn l-lony er aL 2001.11“. 310. 1030).
364 Carbonaeeaus Grains

Table 12.3
Infrared spectral features due to simple functional groups in
btmunoid mmatics

Group u(crn ') Mum) Mode

—CH 3030 3.3 Stretch

370—900 11.3 Out-of-plane bend
—-CH; 2925 3.4 Asymmetric stretch
2863 3.5 Symmetric stretch
1465 6.3 Asymmetric deformation
1375 1.3 Symmetric defamation
1040 9.6 Rocking
—OH 3640 2.75 0—1-1 stretch
1350 1.4 0H deformation
1265 1.9 C—O stretch
-—CHO 2360 3.5 C—-H stretch
2140 3.65
1700 5.9 C-—-O stretch
1390 1.2 CH rock
-—NH2 3450 2.9 N—H stretch
3330 3.0 N—H stench
1610 6.2 NH; deformation
1300 7.7 C-—-N stretch
500 12.5

Adapted from Duley and Williams 1951. MNRAS. 196. 169.

as 0. N, S. and so on. Even in a C-rich environment. it is difficult to imagine that

an abundant and reactive element like 0 can be kept isolated from the grains For
example. 0 atoms can be easily incorporated in C molecules as ketones.
In addition to H, various molecular groups can be attached to the C ring skeleton.
Examples of common side groups (Fig. 11.12) include methyl (—CHJ), methylene
(—CH2—). carbonyl (C=0). aldehydic (—HCO). phenolic (OH). and amine (NI-12)-
Phenolic OH groups bonded to aromatic rings have bands at 2.9 urn. whereas H20
has bands at 2.9 and 6 pm (Fig. 12.1). A parlial list of bands due to functional groups
attached to aromatic compounds is given in Table 12.3.
The existence of side groups can often be uniquely confirmed because their char-
ac teristic infrared bands do not change from one compound to another. For example.
the stretching (Fig. 12.6) and bending modes of the aliphatic groups CH31CH2 at 3-4
and 6.9 urn. respectively (Table 12.2). were first detected in absorption toward the
galactic center by 1010. and have also been observed in the spectra of reflection neb-
 12.! The Aromatic Infrared Bands 3155

.035 ......... I ......... . ......... 1 . ......

rlrrsr
tlfi—rlllrllrrrrlrrrr|r
0.00

IJ_I_I11I_IIlIIIJIjl
Optical depth
p
0
Ln

Aromatics
.0
.—
c:

0.15

0.20 11111 I . I ......... | ..... r 1 - . I ......

Wavelength (microns)

Figure 12.9
150 SWS spew-um (continuum divided) of the GCSS (located at ~ 14 arcmin northeast of the
galactic center) showing the aliphatic hydrocarbon features at 3.4 Iurn and the aromatic C—H
stretch at 3.23 pm (from Chiar et at. 2000, ApJ. 537. 749).

ulae. protoplanetary nebulae, active galactic nuclei, and Seyfert galaxies. Figure 12.9
shows the 3.4-um C—H stretching modes of methyl (CH3) and methylene (Cl-12)
groups in absorption against the continuum of the galactic center. The correspond-
ing asymmetric and symmetric CH deformation modes (Section 8.2.1) at 6.35 and
7.25 out have also been observed in Sgr A‘. These results suggest that aliphatic hy-
drocarbons are widespread in the diffuse ISM, and their detection in protoplanetary
nebulae suggests that these materials may have been synthesized in evolved stars and
ejected into the ISM.
The possible role of oxygen is particularly interesting. Oxygen is the third most
abundant element in the Universe. Even in a carbon-rich environment where most of
the O atoms are expected to be tied up in C0. 0 should still be present as members
of side groups. Aldehydes have a characteristic doublet due to the C—l-l stretch
at 3.55 and 3.67 um. and an example of an aldehyde side group attached to an
aromatic compound can be seen in the spectrum of IRAS 21232+5050 (Fig. 12.10).
The C=0 stretch of aldehyde and ketone (O=C=C) is expected at ~ 5.8 pm (Table
12.1). Emission features at 7.7 and 8.6 tun attributed to the ketone group have also
been seen in the spectrum of QCC exposed to air (“oxidized"). In addition to the dark
QCC that forms in the plasma beam itself. filmy QCC of a light yellow and brown
color is also found on the walls of the vacuum chamber. This filmy QCC is easily
366 Carbonaceous Grain:

8-0 I I l I I T l I I I I I I I I I I .‘__1

21232+5050 3-29 3.29.- aromatic

- C—H MI) '
7-0 — 3.40: asym. cur cn3 —
L 3.46: lone C—H group -
A 6.0 3.51: symmetric Cl-l2 -
"m ' 3.56: aldehydes c.“ m _
’3 5.0 - __
E
u
EP . _
2° 4.0 — -
£3 - ..
:1 3.0 — ._
‘i - c

2.0 — _

1.0 - _.
'- l I I I _l l I I I I a I I_I I I 1 I I ‘

3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.3 3.9 40
Wavelength (pm)

Figure [2.10
A spectrum of IRAS 21282+5050 taken at the Keck Telescope showing the 3.56-um future
possibly attributed to Ihe aldehyde group. in addition to the 3.4mm aliphatic features.

oxidized and polymerized at room temperature. To what extent these ketone groups
contribute to the observed AIB features at 7.7 and 3.6 mm (attributed to the C—C
stretch and C—H in-plane band, respectively. Table 12.2) is not certain. In addition.
while the 6.2-um band is attributed to aromatic ring stretching. it may also contain
contributions from the stretching of the C=O bond. If this is the case, then 0. in
addition to C and H. plays an important role in the structure of carbonaceous grains.
As plastics can disintegrate under sunlight. peripheral side groups can be stripped
from aromatic rings through photodissociation. In the presence of UV light (e.g.. in
a PDR). absorption of photons with energy exceeding the bond energy can result in
the ejection of unsaturated radicals (e.g.. CH. CH2. CH3) from the aromatic ring.

12.2 The 217s-A Absorption Feature

The prominent feature in the extinction curve (Fig. 10.2) was discovered by early
rocket and satellite UV observations of reddened stars. The correlation of the strength
of this feature with the reddening suggests that it is of interstellar origin. The femur:
was extensively observed by the IUE satellite and is found to have a rematiablc
constancy in its peak wavelength (2175 A :1: 5 25%, corresponding to 5.? eV OI
4.6 um” ).
 12.3 The Dlfi‘iue Interstellar Bands 361

The strength of the interstellar absorption feature at 2175 it requires that the
carrier be made of abundant elements such as C. Mg. Si. Fe. and so on. Carbonaceous
materials, being prevalent in the ISM. are considered to be excellent candidates.
Althoagh C-rich AGB stars are believed to be the major supplier of interstellar
carbonaceous grains. the 2175-151 feature is not seen in the Spectra of carbon stars.
This suggests that the carrier of this feature is produced in the difiuse ISM. possibly
after processing by UV radiation and shocks. If the 2175-11 feature arises from a
carbonaceous material. then one would expect this feature to be weaker in a metal-
poor environment. The study of extinction laws in the Magellanic Clouds. which have
much lower metallicitiec than the Galaxy. confirms that this is indeed the case. The
strength of the 2175—151. feature decreases from the Galaxy to the Large Magellanic
Clouds (LMC) to the Small Magellanic Clouds (SMC). approximately in proportion
to their respective CIO abundance ratios.
The 2175-5 feature has long been attributed to absorption by small interstellar
graphite grains. arising from the rr — n‘ transition of sp2 carbon. Another resonance
due to a — a" transition occurs at 800 A. which could be responsible for the rise of
the extinction curve toward the UV. However. a good model fit of observed data with
graphite can be achieved only with fine tuning of the optical constants and particle
sizes and shapes. It has been suggested that a complete surface reconstruction to the
sp2 carbon in diamond can delocalize the it electrons and create a surface mode
analogous to that of graphite. The strong absorption coefficient of diamond in the UV
can also make diamond a contributor of extinction in the UV. Absorption spectroscopy
of carbon onions (Section 11.3.1) shows a feature at 4.55 :|:0.l rim" with a width
of 1.2—1.6um'1. This coincidence. together with the stability of carbon onions.
suggests that they could be the carriers of the 2175-151 feature. Since photoreflective
measurements of anthracite produce a close fit to the 2175-5 feature. the possibility
that this feature arises from a complex carbonaceous compound cannot be ruled out.

12.3 The Diffuse Interstellar Bands

The drama interstellar bands (BIB) are absorption bands formed in interstellar clouds
seen against the spectra of stars. Since their initial discovery in 1922 and the identifi-
cation of their interstellar origin in the 19305. over 150 bands from near UV to near
IR have been detected. The strongest D13 is at 4-429 151. with a width of nearly 30 A.
It is also peculiar that no strong DEBS are found in the ultraviolet. Figure 12.1 I shows
a simulated spectrum of DlBs. We can see that the lines are clustered between 4-400
and 8000 A. correSponding to energies of 1.5—2.8 eV.
Although the bands show a variety of widths. strengths. and profiles. they share
the common property that they are all too broad (FWHM ~ 0.6—40 A) to be attributed
to atomic lines. Consequently. molecular and solid-state origins have been extensively
studied. The invariance of the wavelengths and the narrowness of some bands suggest
that the carriers are gas-phase molecules.
No matter what the carrier of the D135 may be. they must be made up of abundant
elements because the total amount of interstellar absorption due to all known DlBs
368 Carbonaceaus Grains

Spectrum of diffuse interstellar bands

'I ......... I.rv1—rvv—r'.-—rv1-uru—I—..-—IV

LOO

Iffi'fillr‘lellIfi—li‘lllllllIIIIIIIIII1
p
3
Non-nalisedspectrum
an
o
9

0.70

O.wlll_Llllellll ......... I ......... I...I

Wavelength (A)
Figure I2.ll
A simulated spectrum of DlBs based on a catalogue of observed DIBs with each line smoothed
as if observed with a Z-A resolution instrument (from Jennisltens and Désen 1994, Act-AS,
106. 39).

is very large. The most likely candidates are carbon compounds. with carbon chains,
ionized PAl-ls. fullerenes. or fulleranes being some of the proposed carriers. Many
organic molecules have spectroscopic properties similar to those of D135. and it is
quite possible that the D13 carrier may turn out to be complex organic molecules.

12.4 Extended Red Emission

Extended red emission (ERE) is a broad (AA ~ 800 A) emission band with a peak
wavelength between 6500 and 8000 A. ERE was first detected in the sputum oi
HD 44179 (the Red Rectangle) and is commonly seen in reflection nebulae. ERE has
also been detected in dark nebulae. cirrus clouds. planetary nebulae. H II regions. the
diffuse interstellar medium. and haloes of galaxies. The central wavelength of the
emission seems to shift from object to object. or even in different locations within the
same object (Fig. 12.12). . _
Since many solids emit visible luminescence when exPOsed to UV light. 1' '5
assumed that ERE. is a photoluminescence process powered by far UV photons
(Section 11.2.7). In the diffuse ISM. approximately 4% of the energy absorbed by
 12.4 Extended Red Emission 369

ll_l_lll_ll_l_[llllTllll

Red Rectangle

: l i
20— i I —40
E

s r ‘ ‘
g _
"E 6‘50““‘1

E“ _ (1.06)
r-élo— -20

l: — -I

10" south
(1.00)

littlJ_LJ_tiIIIiiml_L
5000 6000 7000 8000 9000
Wavelength (A)

Figure 12.I2
The profile of ERE emission in the Red Rectangle. There is an apparent difference of the profile
at two locations: [0 aruec south (intensity on left ordinate) and 6 arcsec south (intensity on
right ordinate). with peak wavelengths at 16590 and 6839 A. respectively (from Witt and
Boroson 1990. ApJ. 355. 132).

dust at wavelengths below 0.55 pm is emitted in the form of ERE, Suggesting that
the carrier of ERE must be a major component of the interstellar grains. It has been
estimated that the intrinsic quantum yield of ERE is as high as 50%. and the ERE
carrier intercepts ~ 20% of the photons absorbed by interstellar dust in the 900—5500
A range. This limits the chemical composition of the ERE carrier to a few abundant
and highly depleted elements. such as C, Fe, Si. and Mg. Since metals do not undergo
photolumineseenee. the most likely candidates are C and Si.
Proposed carriers of the ERE include HAC, QCC, C60. and silicon nanoparti-
cles. In a material with mixed aromatic and aliphatic composition such as HAC, the
tunneling of excitation energy from one aromatic ring to another is inhibited by the
presence of sp3 material. resulting in wider band gaps. Orange-red fluorescent emis-
sions peaking from 6700 to 7950 A are found in the spectra of QCC (Section 1 1.3.2).
370 Carbonaceous Grains

Since this fluorescence rapidly decays upon exposure to air. it suggests that the fluo-
rescence is caused by radicals and highly unsaturated molecules in QCC, CrySllllinc
silicon nanoparticles with 15-50 A diameters have been suggested to M the
optical properties to satisfy the spectral and quantum efficiency requirements. Exper.
imental studies have shown the silicon nanoparticies can have quantum efl-‘rciencia
near 100% and absorption coefficients ten times higher than average interstellar dun
Because the number of surface atoms relative to the number of volume atoms is hi i
for nanoparticles. in order to avoid nonradiative recombination (Fig. 11.10) all the
dangling Si bonds at the surface of the nanocrystal are passivated by H or 0 atoms.
The key to the identification of the carrier of ERE may lie in the narrow, Sharp
features seen above the continuum. In the spectrum of the Red Rectangle, prominent
narrow features can be seen at 5799. 5823. and 5853 A (Fig. 12.13). The origin of

0.3 : ' _' f I 1— -

= :l
0.7 ; i
0.6 g— -§
5 0.5 r ':
= 0.4 E ':

0.2 '—
=. II ' I '. l. H I | I I -I5
°-'s s ”2 :°:*- a e ere-e: 2-: s - - °- ‘=
0.0g 'l n
s is
I; L
sEsE Es Massage 2»:l 4‘ 4L 4 L J_ 1
3 J
E a '

—0 56m 5700 5300 5900 6000 61m 62m

A (A)
__ I I I A

0.03 - _
_ 4
- 1
K -

§u 0.02 _- J.
a: _ -

- 1
0.01 - 'g‘ j
1 AL A_L I_A J_- L l_.¥‘ ‘41 A_L 1 1441—4 I 4L gk? 4 I l I l J

5600 5700 5800 5900 6003 6l00 62m 6300 64m 6500 6600 67m 6300
“A;
Flat-re I113
Narrow ERE emission features in two locations in the Red Rectangle. Top: 6 aruec from the cenu'al
star; bottom: It tune: from the central star. Wavelengths are corrected for the velocity of the Red
Rectangle (+139 km ") (adapted from Van Winckel er al. 2002. AM. 390. I47).
 I25 The ZI-um Feature 371

these narrow features is unknown, although the coincidence in wavelengths between

some of these features with DIBs has led to the suggestion that the ERE and D185
share the same carrier.

12.5 The 21—pin Feature

The strong emission feature at 21 aim was first discovered in four protoplanetary
nebulae from observations by the IRAS Low Resolution Spectrometer (LES). High-
molution (HA1 = 2000) ISO observations have found that all features have the same
intrinsic profile and pealr wavelength (20.l rim) (Fig. 12.14). There is no evidence for
any discrete substructure due to molecular bands in the observed spectra, suggesting
that the 2 l-um feature is due to either a solid substance or a minute of many similarly
structured large molecules.
The fact that all of the Zl-um sources are carbon rich strongly suggests that
the cadet of this feature is carbon-based. Since the MB emission features are also
seen in the Zl-um sources, it is likely that the carrier of the Zl-flm feature is related
to aromatic ring carbon compounds. or even larger molecules that might form from
such compounds. Possible candidates that have been proposed include large PAH
clusters, hydrogenated amorphous carbon (HAC) grains. hydrogenated fullerenes.
nanodiarnonds. TIC nanoclusters. nano-SiC grains with carbon impurities. cold SiC
grains with amorphous SiOz mantles, and so forth.

250'— l I ‘l’ '7 r I fil r I

07134+l005 1
200 —|
=3; .l _
N I

5 150 'I \J —
. I I
a? I .i ’fi'fikl, '

‘2 100 . «J 'ffiv‘.‘ -—

5* #‘r it; ~
50 ; Mu -—

0 I
at
I I I J I I I
It I

0 lo 20 30 40 50
Wavelength ( pm)

Figure 12.14
ISO SWS spectrum of the protoplanetary nebula IRAS 07l34+1005 showing the strong
unidentified Zl-um emission feature (from Kwok 2004. Nature. 430. 985].
372 Carbonaceou: Grains

12.6 The 30-,um Feature

The unidentified emission feature around 30 pm was discovered from m0 0mm

vations. It was first seen in carbon-rich asymptotic giant branch (AGB) stars (mg,
IRC+102l6 and AFGL 2683) and planetary nebulae (e.g., lC 418 and NGC 6572):
Figure 12.15 shows that the Clo-um feature is very prominent in NGC 7027. Mo“:
recently. the 30-pin feature is found to be common in carbon-rich protopl
nebulae, especially those showing the ill-um emission feature. Figure 12.16 shows
the ISO spectrum of the SO—ttm feature after the removal of a continuum. The feanue
is broad and may consist of subfeatures at 26 and 33 am.
The origin of the 30-pin feature is not known. The fact that a significant fraction
(~ 20%) of the total luminosity of the object is emitted in this feature suggests that
the carrier must be composed of abundant elements. The first suggested identification
was solid MgS based on a comparison with laboratory measurements. The altemafivc
suggestion that the carrier is a carbonaceous material continues to be popular because
the feature is seen only in carbon-rich objects.

10L 4 - I 1 l l 1 1 l l u 141 1 - ' I

1 [0 [W
Wavelength (pm)

Flgure 12.15
“Die [30 SWS/LWS Spectrum of NGC 7027 between I and 200 pm. Some of the stronga’
atomic lines and A113 features are marked. The dashed line is a model fit composed of a sum of
dust emission (at = l). and f-b andf-f gas emission. The strong Ito-um feature can be clearly
seen above the dust continuum.
 12.7 Plateau Features 373

t 1 I 1— ]

19500-1709

SWSOIEWSOI
—— W506
- PHT-S
Emission profile

l 1 1 _.L 1 1 ,

20 30 40
Wavelength (pm)

Figure 12.16
The 130 SW501 . 5 W506. LWSOI , and PHT—S spectra of IRAS 19500-1709 showing the 30-um
emission feature after the removal of a continuum (from Vollt «01.2002, ApJ. 567. 412).

12.7 Plateau Features

In addition to the infrared emission bands attributed to aromatic and aliphatic suuc-
tures (Table 12.2), very broad emission features at 3 and 12 um are seen in the spectra
of protoplanetary nebulae (Fig. 12.17). Since the 6.9-,um band is known to originate
from a mixture of —CH2—- and - -—CH3 bending modes (Table 12.2. Section 12.1.1).
associated bending modes of other side groups can also be presem. Examples include
the —C(CH3)3 bending modes at 8.16 pm (Fig. 12.18. site “e“) and the =C(CH3)2
(Fig. 12.18. site "1") bending mode at 8.6 urn. These features together can form a
quasi-continuum similar to the observed broad feature.
Similarly. the 11.3-urn aromatic out-of—plane bending mode (Section 12.1) can
be accompanied by a complex set of features due to out-of-plane vibrations of alkenes.
Such groups can be connected directly to the aromatic rings (e. g.. the —CH=CHCH3
group at site "a” of Fig. 12.18), or indirectly (—-CH2CH=CH2; Fig. 12.13, site "b")
through an alkyl (CH2),, linkage to aromatic rings. Cyclic alkanes (—CHZCH2Cl-l1—:
Fig. 12.18. site “c") may also contribute in the short-wavelength part (9.5—1 1.5 pm)
of this band. and long chains of four or more —-CH2— groups (——(CH2)4CH3;
Fig. 12.13, site “d") may contribute to the long-wavelength end (13.9 urn).
 5 '69 l m l ' f ' l E
was 222724-5435 J
5_ 62‘ ISO swsm
J I 17 6.2: sp’ C=C stretch
- ll 6.9: sp? C—H bend -
4 __ l 7.7: if C—C stretch
Ratioed spectrum l. l l .4: .sp2 C—H out-of-plane bend H
l2. l: .5302 CH out-of-pllne bend i

,3.-

'5!
I
l_' _l—‘_ I

.—c""""".

L
"—9)
J}
N

a
.4

a“. j

0 _1 I _l_ _l_ l _l_ l l 1

U 10 20 30 40 50
Wavelength (pm)

Figure 12.17
The ISO SWSOl spectrum of the pmtoplanetary nebula IRAS 222721-5435 after the removal of
a continuum The detected narrow emission features and their peak wavelengths are marked
on the spectrum. The identifications of some of these features are listed in the legend (from
Kwok et at. ZWI. ApJ, 554. L37).

Figure 12.18
Schematic chemical diagram illustrating the various possible side groups mashed to aromatic
rings that contribute to the plateau emiSSions (from Kuwait e: at. 200LApJ. 554. L37)-
 12.8 Photochemistry 375

Figure 12.19
A schematic illustration of the C—-C-—C in-plane bending mode of an aromatic molecule
(from Van Kerlthoven er al. 2000. AM. 357, 1013).

The existence of the plateau emission features therefore suggests that the structure
of these carbonaceous grains is complex. and probably includes a variety of alkane and
alkene side groups attached to aromatic rings. Comparison between the astronomical
plateau features seen in Figure 12.17 to the infrared spectrum of semi-anthracite coal
shOWs a lot of similarity, suggesting that the carbonaceous grains in protoplanetary
nebulae may have similar chemical structure with coal.
Another broad plateau emission feature from 15 to 25 um has been detected in the
ISO spectra of H tr regions. young stellar objects, and planetary nebulae. This broad
feature has been attributed to blended emission features arising from the C—C—C
in- and out-of—plane distortion of the carbon ring (Fig. l2.l9).

12.8 Photochemistry

The photochemistry of complex organic molecules has been studied extensively by

physical organic chemists. When gas-phase alkanes absorb UV light. the primary
photochemical event is the elimination of molecular hydrogen to form alkenes. Minor
channels are the cleavage of C—H and C—C bonds to form free radicals. Alkenes,
in contrast, have a much richer UV photochenustry. They undergo a variety of
isometimtions. bond migrations. and cyclization reactions. Of particular interest are
the ring closure reactions and cycloaddition reactions that transform alkenes into
ring systems. Additional hydrogen loss can then result in fully aromatic rings that
are more stable than alkanes or alkenes. The net result of UV irradation is thus the
transformation of aliphatic to aromatic groups.
For heterogeneous cOmpounds such as HAC or coal. the absorption of photons
with energy higher titan the bond energy can result in the ejection of molecular
fragments from the aromatic cluster. Some examples of the bond energies in HAC
are given in Table 12.4.
376 Carbomceous Grains

Table 12.4
Average bond energies in HAC

Bond type Energy (eV) )t (um)

C(sp3)—C(sp3) 3.61 0.340

mph—cup!) 3.70 0.335
C(sp2)-ctsp1) 3.91 0.317
C(spJ)—H 4.31 0.290
C(sp1)=<:(sp1) 6.12 0.135
11—1-1 4.74 0.262
R—CH, 4.02 0.303
11—1-1 4.52
H—CH3 4.53
H—czH 5.36

A is the short-wavelength threshold for photodissociation.

R is aromatic (C6) ring (from Dulcy 2000. ApJ. 528. MI).

12.9 Summary

Infrared spectroscopy represents a new powerful tool in the identification of solid-

state componds in space. The observation of a number of unidentified emission
and absorption features implies that there exist materials in the circumstellar and
interstellar medium that are unfamiliar to us in the terrestrial laboratory environment.
The identification of these features and the deterrninatiOn 0f the chemical nature of
their can-iers not only enhance our understanding of the physical conditions in space,
but also open new frontiers in the understanding of fundamental chemical processes.
We now believe that carbonaceous grains are widely present in the ISM. Through
infrared spectroscopy. the stretching and bending modes of aromatic and aliphatic
compounds have been identified. A variety of unidentified features, including the
ZITS-A feature. the ERE. and the 2l- and 30-“.[11 emission features. are suspected
to originate from carbon-based materials. Where and how these carbonaceous grains
are synthesized is therefore a major question to be answered. Because of the different
conditions under which they are formed, these carbonaceous materials may be quite
different from natural substances found in the terresu-ial environment. The discussion
on the origin of interstellar grains, and the physical and chemical processes that lead
to their creation. is the subject of the next chapter.

Further Reading

Kwok. 8. (ed.) l993. Astronomical Infrared Spectroscopy: Future Observational Dim:-

tt'ons. ASP Conf. Ser. 41.
Witt. A. N.. Clayton, G. C.. and Draine. B. (eds) 2W4, Astrophysics of Du“. ASP COM-
Scr. 309.
A
The Origin ofInterstellar Dust

Micron-size dust particles made up of millions of atoms are widely observed in the
ISM. How did these grains condense from atoms in the gas phase? Where were they
first formed? Did they undergo physical or chemical changes during their voyage
through the ISM? Why are only certain kinds of solid materials made? Since comets.
meteorites. asteroids. the ten'estrial planets. and Earth are just larger aggregates of
solid material. are these solar system objects chemically related to interstellar grains?
The understanding of the chemical and physical origins of interstellar grains are.
therefore. of great importance.
Modern observalions spanning from the infrared to the ultraviolet have imposed
major constraints on the composition of interstellar dust. These constraints consist
of the extinction curve. scattering properties. polarization. emission and absorption
features. and the shape of the infrared emission continuum. The dusr composition is
also constrained by the abundances of refractory elements and the observed depletion
levels of these elements in the gas-phase ISM (Fig. 10.1).
The deteetion of silicate and SiC grains in the respective surroundings of oxy-
gen and carbon-rich AGB stars suggests that grains can form in the upper stellar
atmospheres. Once formed. they are ejected by radiation pressure into the ISM (Sec-
tion 15.7.1). Grains have also been detected in the circumstellar envelopes of novae,
supernovae. and Wolf-Rayet stars. The condensation process must be extremely effi-
cient once the condensation temperature has been reached: for example. novae have
been seen to develop the silicate feature from a featureless f-f infrared continuum
over a period of a few days. By fitting the spectral energy distributions of AGB stars
(Fig. 11.1). one can derive the rate of grain ejection to be typically 10 a Mo. yr" '.
Multiplying this rate by the number of mass-losing AGB stars in the Galaxy. ~ 10‘2
M3 of grain material is injected into the ISM every year.
While the formation of solid-state materials is directly observed in the circumstel-
Iar environment, it is not clear to what extent these grains are processed by interstellar
UV radiation. cosmic rays. shocks. and cold, dense gas in molecular clouds. However,
the recent detection of stellar grains in the solar system has shown that at least some
stellar grains can survive the journey through the ISM (Section 13.5).

317
378 The Origin offerersrellar Dust

13.1 The Formation of Dust in the Atmospheres of AGB Stars

In the circumstellar envelopes of carbon stars. molecular species of a wide vafi

of complexity have been discovered. from simple molecules such as C2 and CN (by
optical spectroscopy). C0 (infrared and microwave spectroscopy), C2H2 (infrared
spectroscopy). to long linear molecules such as HC5N (by microwave Specuoscopy)
and solid-stale compounds such as SiC. In extremely evolved carbon slat-5‘ the in:
frared continuum is primarily featureless. and is believed to be due to amorphous
carbon (Section ”.32). Since the dynamic ages of the circumstcllar envelopes are
only ~ [04 yr. it is clear that chemical processes are extremely efficient in transform.
ing simple molecules into complex structures. One can imagine that the chemical
pathway begins with synthesis in or near the photosphcre with simple molecules such
as CO. HCO". and Czl-lz. and then progresses to the formation of carbon chains of
unsaturated hydrocarbons (CHI-1,... :1 << m) and cyanopolyynes (HCHN) in the cit-cum.
stellar envelope. Further growth in carbon-based molecules will take place With the
formation of a and Jr bonds.
Based on principles of thennodynamics. one envisions that grains can form in
the atmospheres of AGB stars as the wind flows outward and cools. The first step is
to create a critical cluster that serves as a seed for condensation. This is followed by
molecular accretiOn and grain growth. Possible seeds that have been suggested include
M203 and 1102 (Section I 1.2.3. Fig. 13.1). The accretion of atoms (e.g.. 0, Mg. A],
Si. and Fe) and molecules (OH. H20. 0;. SiO. AIH, AlOH. FeO. MgO, MgOH. SiO.
SiH. etc.) leads to the formation of mantles of composition SiOz. A1203, MgAl104.
MgISiog. Fe203. and so on.
For O-rich stars. excess 0 atoms. left over from the formation of C0. react with
Al. Fe. Si. and Mg to form silicates and other metal oxides. Although details of
the nucleation process are unknown. it is anticipated that the formation of silicate
dust begins with the formation of SiOJr clusters. The question of whether these
clusters will grow into monomineralic crystallites. humogeneous amorphous solids
with short-range order similar to glass. heterogeneous solids with mixed crystalline
and amorphous layers. or chaotic silicates (Section 13.3) is yet to be answered.
Our general everyday usage of the tetrn “dust" refers to all kinds of minute
particles including earth blown up by wind. pollens from plants. particles from
volcanic emptions. as well as products of combustion. Since circumstellar grains are
condensed from gas-phase molecules. it has been suggested that it is more appropriate
to refer to circumstellar grains as “smoke" rather than “dust." Our general use of the
term “smoke" refers to residues of incomplete combustion of complex organic matter.
and is therefore also not an exact analog of gas-phase condensation. However. our
understanding of the dust nucleation and condensation in stellar atmospheres is still
mdimentary. and it is possible that the process in fact resembles combustion.
In a C-rich environment. the condensation of carbonaceous matter probably be-
gins with the gmwth of Con SiC seeds. When the gas is cooled to 1100 K. the aromatlc
molecules formed in the gas phase will condense onto the surface of these particles;
The emergent material is likely to contain a different fraction of sp. sp2. and 5P
 [3.2 Models ofChrbanaceaus Dust 379

2200

2WD
Condensation temperature (K)

IBOO

I400

l200 - Jib 4’30,» _

L °° -
l l I l l I l l I l I I I

”m .2 —4 —6 —s —lO —12 —I4

logm Pu (bars)

Figure 13.1
Condensation temperatures for various carbides and graphite as a function of total pressure and
C10 ratio (from Ladders and Fegley [997. in The Astrophysical Implications ofrhe laboratory
Study of Pnsalar Materials. eds. T. Bematowicz and E. Zinners. Am. lnsL Phys. Conf. Proc.
402. 38]].

sites. forming amorphous or kerogen-like compounds. As the radiative environment

changes. graphitizalion of these compounds is a possibility (Seetion 12.8).

13.2 Models of Carbonaceous Dust

An example of possible structures of carbonaceous grains including both aromatic

and aliphatic components is shown in Figure 13.2. Among the 470 C atoms in this
380 The Origin ofinrerrreliar Dust

OCarbon . 11'I:
a Hydrogen _ - -.
0 Oxygen I»? . _ *I 1" 2 c I,
O Nitrogen ' , ‘ ‘I 7

[H j .,
I'II'I‘I 4 ° ' - .
U - I
. g 03:39: g . '-
r ' _‘ r ‘

’ eO o O0:0...
.0
" .. " 00".
.“. 3
o ' ' '3‘”
° ~' f
'2) 5
O. i .-
p__

0 Carbon
e. Hydrogen
0 Oxygen
I Nitrogen
I—l
0-5 nlfl l. Aromatic 2.Aliphalic 3. Aliphatic 4. Aromatic 5.Aromnlic
network bridge carbonyl carbonyl nitrogen

Figure 13.2
A model of carbonamous interstellar dust consisting of various aromatic and aliphatic groups.
Examplcs of five basic units are shown in the bottom of lhc figure (from Pendleion and Allamar'rdoll
20in. ANS, I38. 75).
 13.3 Laboratory Simulations ofCormt'c Dust 331

structure. 400 are in aromatic units and 70 are in aliphatic groups. The approximate
volume of this structure is ~ 10 ’9 cm3. so approximately If)4 of such structures will
be contained in a typical grain of 0.1 #111-
Such a schematic gives only a sketch of possible structures of carbonaceous
dust as we are able to discern from spectroscopic observations. Our lack of precise
knowledge of the structure of interstellar dust should not be surprising. considering
the fact that the structure of one of the most common substances of high commer-
cial value—coal—is not well determined. This is in spite of the fact that we can
subject coal to a variety of techniques for laboratory analysis. including infrared ab-
sorption spectroscopy. magnetic resonance spectroscopy. X-ray diffraction. electron
spin resonance. mass spectroscopy, ultraviolet spectroscopy. and electron microscopy.
All we know is that. in general, coal consists of a macromolecular network of are-
matic ring clusters linked by bridges. mixed with a component of lower molecular
weight species. Similar uncertainties apply to the nonvolatile component of petroleum
residua. Even when we are able to collect interstellar dust particles and bring them
back to the Earth for laboratory analysis. we may have to face the possibility that we
may not be able to define their structure.

13.3 Laboratory Simulations of Cosmic Dust

The identification of the chemical composition of interstellar grains relies on com-

parison between the observed spectral signatures and laboratory measurements of
ten'estrial counterparts. However. since interstellar and terrestrial conditions are very
different. it is not certain that interstellar grains will have exact terrestrial counter-
parts. Even for the most commonly observed grain in the ISM (amorphous silicates).
we do not yet have an exact counterpart of such grains in the laboratory.
In the past three decades. there have been increasing efforts to simulate interstel—
lar and circumstellar conditions in the laboratory. and to use a variety of techniques
to create artificial substances that bear Spectral resemblance to the observations. Be-
ginning with a mixture of gas-phase molecules with appropriate cosmic abundances
and subjecting this mixture to external energy sources. new and unknown compounds
can be synthesized.

13.3.1 Silicates
While there is no doubt that the 9.7- and lB-um features are respectively due to the
stretching and bending vibrations of Si—O and O——Si-—0 bonds of submicron-size
grains. the exact structure of astronomical silicates (other than their amorphous na-
ture) is not known. They almost certainly contain some silicon—oxygen tetrahedra.
but these units may be scattered in an amorphous solid with varying compositions.
They could also contain regions of underoxidized silicon that are not part of the
silicon-oxygen tetrahedra. Such grains would be more chemically active than terres-
trial silicates. and the term “chaoric silicates" has been used to describe these exotic
solids. The best way to answer these questions is to make laboratory simulations of
such solids.
332 The Origin oflrrterstellar Dust

Techniques to reproduce amorphous silicates in the laboratory include the e

oration and recondensation of crystalline silicates in an electric are. by laser pulses
and by thermal heating. Amorphous silicates have also been produced by Precipimfior:
from solutions, irradiation of crystalline silicates with rare gas ions. and Sputtering of
silicates in an oxidizing environment.
The goal of laboratory simulations is to produce an amorphous silicate that shows
the broad. structureless 9.7- and lS-um bands that are observed astronomically, How—
ever. spectroscopic measurements of the same material using different techniqucs
can yield different results. For example. optical data determined by reflection spec.
troscopy can differ from those obtained by transmission spectroscopy. The effect;
of grain size and temperatures also make comparisons with astronomical data more
problematic. since both size and temperature are known to change the strengths and
profiles of the bands significantly.

13.3.2 Carbon Grains

A variety of techniques have been used to simulate the production of carbon dust in
the laboratory. QCCs are synthesized by quenching the plasma of methane (CHO gas,
HAC films are prepared by laser ablation of graphite in a hydrogen aLInOSphere. Scots
have been produced by hydrogen flame or arc-discharge in a neutral or hydrogenated
atmosphere. Infrared laser pyrolysis of gas-phase molecules (C311... C4H6) has been
used to create carbon-based nanoparticles. Soot is formed by combustion of hydro-
carbon molecules in a flame. The exact chemical composition of soot is dependenton
the relative mix of the precursor gas. and the pressure and temperature of the flame.
From this point of view. soot can also be considered as an artificial carbonaceous
compound. The combustion of heavy hydrocarbons in a furnace yields carbon black.
which is also a form of amorphous carbon similar to soot and HAC. Chemically. soots
and HAC are similar in that they are composed of H atoms and sp2 and sp3 carbOn
atoms (with sp’fi/sp2 > I. as in coal). They are different primarily in the mode of pro-
duction. Once hydrocarbons are made in a stellar atmosphere or a stellar wind. it is
possible that soots and HAC can be produced in the circumstellar environment.
The chemical compasirion of coal is lcnown to change with time. The time
evolution from low-rank coals to high-rank coals like anthracite is a progressive
increase of aromaticin where the aromatic—to-aliphalic C atom ratio increases and
the H content decreases (Fig. l3.3). This process can be primarily attributed to an
increase in temperature as coal sinks to greater depths in the Earth's crust. This
chemical transformation has also been reproduced in the laboratory by submitting
coal to annealing.
Once these materials are synthesized. their properties can be determined by a
variety of techniques. For example. scanning electron microscopy is used to determine
the grain shape and size. transmission electron microscopy to determine the internal
structure. electron diffraction to determine the crystalline degree. and electron energy
loss Spectroscopy to determine the electronic properties.
Whether the artificially created subtances such as QCC and HAC play 3 1‘01?
in the natural comp0sition of interstellar dust is dependent on the condition 0f M
 [3.3 laboratory Simulations of Cosmic Dust 333

Increasing aromatization
(b)

N Aliphatic chain
0 Aromatic ring

Figure 13.3
A schematic diagram illustrating the natural transformation of coal (from Alvarez er al. [998.
Energy Fuels. 12. 349).

synthesis. While it has been demonstrated that both QCC and HAC show similar
spectral behavior with interstellar and circumstellar dust. the special conditions upon
which they are manufactured may preclude them as natural products of interstellar
chemistry. For example, HAC is a family of very different materials whose properfies
are very sensitive to preparation parameters (substrate temperature. applied voltage,
gas pressure. etc.) and subsequent heat treatment and exposition to air. Since we
do not have highly controlled laboratory conditions in the interstellarlcircumstellar
environment, it is more likely that the natural products of molecular condensation or
334 The Origin oflnrersrel'iar Dust

combustion are a mixture of compounds involving all abundant elements and not just
H and C alone.

13.3.3 Nanopartieles
Although most of the studies on interstellar grains have centered around miCTOn-sizg
particles. there is increasing interest in particles of smaller sizes (nanopanicles)_ both
from the point of view of synthesis and spectral behavior. In a low-radiation-density
environment such as the diffuse ISM. nanoparticles have the advantage of being able
to be heated by single-photon processes.
Under thennodynamic equilibrium. diamond only can form under high Pressure.
Diamonds were first made synthetically in the laboratory at pressures of 30,000
bars ( 1 bar = atmospheric pressure) and temperatures over 700°C. Natural diamonds
are made in the Earth‘s mantle. at depths of ISO—200 km. and are brought to the
surface via volcanic pipes. A sudden drop in temperature is required in order to avoid
their transformation into graphite. the stable form of carbon under low pressure;
However. laboratory experiments have shown that diamond-like material can be
formed under nonequilibrium conditions. such as during condensation of carbon
vapor on cool substrates. Nanocrystalline diamonds can now be made in the laboratory
under low pressure using the chemical vapor deposition (CVD) technique. Once
formed. diamond is “metastable“ and requires high temperature to convert it to
graphite.
This has opened the possibility that diamond can form in low-density. low-
pressure environments. as in the circumstellar envelopes of carbon stars. Laboratory
Studies have shown that the formation of diamond crystals is facilitated by the presence
of oxygen. One possible route to the formation of interstellar nanodiamonds involves
the hydrogenation of aromatic material (to HAC. for example) followed by exposure
to UV radiatiOn in the presence of oxygen. Another possibility is that nanodiamonds
grew from gas-phase carbon dimer (C2). a molecule that is commonly observed in C
star atmospheres.
Because the mobility of electrons in a small cluster is reduced in comparison
to bulk materials. the spectral behavior of nanoparticles can be quite different from
their bulk counterparts. Because of their small size, the boundaries are important and
they cannot be approximated as an infinite lattice. However. the energy levels of the
quantum states are still spread out enough to be treated as a continuum. Due to the
loss of symmetry. some vibrational modes can be more infrared active than in large
crystals of the same chemical composition.
Laboratory laser-induced plasma reactor experiments involving early transition
metals with hydrocarbons have produced metal-carbon clusters such as TiC (Section
l [2.4). including TigCl 2 (with a tetrahedral structure) and Ti14C|3 (a 3 x 3 x 3 cubic
structure). Both have strong resonances in the ZO-urn region that are not present in
built samples. The exact frequency of the resonance. howwever. is dependent on the
cluster size.
Pre-solar 'I'iC grains in meteontes (Section 13.5.4) have a graphitic mantle and
have sizes of about 500 A. TiC grains of such size and structure have been successfully
 ”.4 UV Processing aflces 385

produced in the laboratory by gas evaporation (the smoke method). However. graphite
mantles are expected to quickly form around the TiC cores. Metal carbides are also
interesting because the hydrolysis of carbides can produce H2, CH4, and a series
of alkanes and alkenes. and may play a role in the formation of hydrocarbons. The
hydrolysis of mixed metal carbides and nitrides has been shown to be able to produce
biologically relevant molecules such as guanldine. methyl hydrazine. formic acid.
hydrogen cyanide. urea. cyanamide. methylamine. formaldehyde. and so on.
Because ofthe different spectral behavior ofbulk materials and nanoparticles. it is
possible that common minerals in small sizes possess strong features in the infrared
that are not known. [I is therefore important for the identification of astronomical
features that further spectroscopic studies of nanoparticles are made in the laboratory.

13,4 UV Processing of Ices

The possibility that the chemical composition of interstellar grains (in particular the
grain mantles. Section [0.10) can be altered by UV radiation has been extensively
studied in the laboratory. Starting with simple ices such as H20, CO. CH4. N'Hg,
CH30H, C2H2, and So on. at low (~10 K) temperamres, an organic substance
called “yellow stuff" can be produced by subjecting the sample to UV radiation and
subsequent warming. When this substance was carried into space and subjected to
fear months of solar radiation, irs color changed from yellow to brown, suggesting
increased absorptivity as a result of increased carbonization. photodissociation. and
depletion of O. N. and H from the sample. The near-infrared spectrum of the final
sample shows the 3.4-rrm feature due to the methyl (—CH3) and methylene (—
CH2) aliphatic groups (Section l2.1.l), as well as broad plateaus around 3 and 6 um
suggestive of the CH stretch in alcohols and carboxylic acids (3 pm). and C=C, C=0.
C—OH, CEN. C—NHI. and similar stretches. to CH, OH. and NH: deformations
(beginning at 5.5 rtm and peaking at 6 pm). These spectral properties of this final
sample resemble those of kerogens extracted from carbonaceous meteorites, and this
final sample was termed organic refractory matter by Mayo Greenberg.
Ultraviolet photolysis of ices containing H20. CH3OH. CO. and NH3 (in ra-
tios consistent with ices in molecular clouds) can create a rich variety of moder-
ately complex organic molecules: CH3CH20H (ethanol). HC(=O)NH2 (formamide),
CH3C(=0)NH2 (acetamide). R—CEN (nitriles), and hexamethyleneretramine
(HMT. CanN4). as well as more complex unidentified organic materials that include
amides 012NC(=O)—R). ketones (R—C(=O)=R’), and polyoxymetlrylenes (POM.
(—CH20—)n), where R is used to represent a generalized alkyl group. l-EMT. which
contains four N per molecule. is one of the major organic residues produced by pho-
tolysis. It has been known since the 19705 that HMT formed spontaneously at room
temperature when pure ammonia and formaldhyde were mixed. Since hydrolysis of
HMT by concentrated acid can yield amino acids, the formation of this molecule in
the ISM has great significance.
336 The Origin ofInterstellar Dust

COOH
at. "m; raw COOH

2 D-Ala
D-2-ABA COOH L-Ala
/ L-Z-ABA
Have ..
HIN K
"2N7
HIN

L-Ala ( 9 to n 12
D-Val + B—Ala
H
L-Val
D-Ala D.L-PI'D
H 1N fl“
' an 2 HJMH
L-Asp
D-Asp D—Ser
N-EtGly "20‘3”":

2.5 5.0 7.5 10.0 12.5 15.0 I7.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 40.0 42.5
Time (min) '

Figure 13.4
Gas chromatogram showing the amino acids (e.g.. Gly. glycine; Ala. alanine; Prol. proline: Val.
valine. etc.) and other compounds (e.g.. DAP. diaminopentanoic acid: DAH. diaminohettanoic acid)
generated in UV radiated ice (from Malta: et at. 2002. Nature, 416. 403).

Ultraviolet photolysis of amorphous water ice mixed with CHJOH. HCN. and
NH3 followed by warming and ice sublimation leaves behind an organic residue that
is found to contain N-fonnyl glycine. cyclosen'ne. and glycerol upon analysis with
gas chromatography—mass spectrometry and liquid chromatography. After hydroly-
sis. glycine. alanine. serine. glycerol. ethanolaminc. and glyceric acid are observed
(Fig. 13.4). Similar experiments using different initial ingredients also yield many
amino acids (Fig. 13.5). These results suggest that spontaneous generation of amino
acids in the ISM is possible.
Similar efforts have also been made to produce nucleic acid bases. which are be-
lieved to be essential for the generation of life. Proton irradiation of carbon monoxide
nitrogen. and water under simulated interstellar conditions has been shown to be able
to yield uracil. one of the four RNA bases (the others being cytosine. adenine. and
guanine). Thymine, the base that substitutes for uracil in DNA. has been reported 10
be preSenl under proton irradiation of a mixture of methane, carbon monoxide. and
ammonia.
 13.5 Interstellar Dust and the Solar System 337

2'?
'E
3

E
.E

8
E

E
E.‘

S l0152095303540455055606570
Retention time (min)

Figure 13.5
High-perfonnance liquid chromatogram of amino acids produced by UV irradiation of an
icy mirrture of methanol. ammonia. and water. The labelled products are Asp: aspartic acid.
Thr: threonine. Ser: serine. Glu: glutarrric acid. AM: aminoadipic acid. Gly: glycine, Ala:
alanine, ABA: aminobutyric acid. Val: valine (from Kobayashi et at. 2004. Advances in Space
Research. 33. 1277).

13.5 Interstellar Dust and the Solar System

Elecu'omagnetic radiation is not the sole source of infon'nation on chemical processes

in the ISM. It is possible that remnants of interstellar grains in the solar nebula were
accreted directly into macroscopic bodies such as asteroids and comets during the
formation of the solar system. Dust particles released by comets enter the Earth’s
atmosphere as micrometeorites and are seen as meteors. Micrometeorites. typically of
sizes 100 to 1000 um. can be collected in the Arctic or Antarctic ice or from sea floors.
Impacts with other asteroids may release debris that subsequently crosses paths with
the Earth and the remnants after passage through the Earth's atmosphere end up on
Earth as meteorites. Fragments ofcomets and asteroids are the source of interplanetary
dust particles that can be captured by high-flying aircraft or spacecraft.
The availability of these extraterrestrial samples in the laboratory allows a variety
of techniques to be applied to study their physical properties such as sizes and shapes.
and chemical compositions. both elemental and isotopic. Examples of techniques em-
ployed include mass spectroscopy. scanning transmission X-ray microscopy. nuclear
388 The Origin ofInterstellar Dust

magnetic resonance spectroscopy. X-ray computed tomography. focused ion beam

microscopy, as well as infrared spectroscopy. It is conceivable that future space mjs_
sions can be sent to the boundary of the solar system and the ISM and directly collect
interstellar dust and measure its chemical and physical composition. This will rename
a lot of the uncertainties inherent in remote astronomical observations.

13.5.1 Comets
Comets were formed in the outer solar system and were later scattered into highly
elongated orbits by the forming planets. Long-period ( P > 20 yr) comets are belieued
to originate from the Don Cloud (IO‘l—lOS AU from the Sun), whereas short-period
(P < 20 yr) comets originate from the Kuiper Belt (30—50 AU).
As they approach the Sun. gases that have previously been in frozen solid
forms are gradually vaporized and released. In the past. it was generally believed
that the outgassing is primarily due to the sublimation of water ice. and comets
are nothing more than "dirty snowballs." Spectroscopic observations have remaled
the presence of H20. C0. HCN. CHJOH. CHJCN. and other molecular species
(Table 13.1). Cometary outflows also centain solid particles. which can be detected
through scattering and thermal emission. Infrared signatures of silicates (Fig. ll.3)
and carbonaceous grains have also been detected (Table 13.2). For example. the
aliphatic C—H stretching modes (Section 12.1.1) can be seen in the spectrum of
Comet Swift—Tuttle (Fig. 13.6). These detections suggest that interstellar molecules
and grains were already present in the solar nebula from which comets condensed.
In addition to remote observations. in situ measurements of cometary dust are
possible with space missions. Time-of-flight mass spectrometers onboard spacecraft
sent to intercept Comet Halley in I986 have measured 5000 particles, giving valuable
direct information on the chemical composition of cometary dust. These mass spectra
reveal the presence of heavy rock-forming elements such as Mg. Si. Ca. and Fe. as
well as light elements H. C. 0. and N. The former group suggests the presence of
inorganic minerals whereas the latter group is consistent with the presence of organic
refractory material.
These observations have drastically changed our understanding of the origin
of comets. Instead of being condensates out of a homogeneous solar nebula that
has vaporized all pre—solar material. we now believe that comets are the result of
direct aggregation of molecules and dust that have been delivered to the solar nebula
from stars and molecular clouds. Consequently. comeLs preserve the most primitive
materials from the early solar system. SpaCe missions to comets allow in situ analysis
of dust compositions in comets through mass spectroscopy. yielding both size and
elemental abundance determinations. The observations or sample gathering from
comets therefore repreSent a link to the production of solid-state matter in stars.

13.5.2 Interplanetary Dust Particles

Dust panicles in interplanetary space have long been known from zodiacal light. From
thermal emission and scattered visible light measurements, we know that the zodiacal
light originates from dust particles located on the ecliptic plane at distances between
0.3 and L7 AU from the Sun. lnrerplanetarjv dust particles (IDPs) are fragments
 [3.5 Inlerslellar Dust and the Solar System 389

Table 13.1
Examples of molecules observed in comels and their
abundances

Molecules Relative abundance Technique

H20 l00 1R
C0 20 Radio. IR. UV
C02 6 IR
CH. 1 IR
C2H2 0.5 IR
C2H‘ 0.5 [R
CHJOH 2 Radio. 1R
H‘ZCO 1 Radio
HCOOl-l 0.05 Radio
HCOOCH; 0.05 Radio
NH} 0.6 Radio
HCN 0.2 Radio. IR
HNC 0.03 Radio
CH_\CN 0.02 Radio
HCJN 002 Radio
HNCO 0.1 Radio
NHZCHO 0.01 Radio
HIS 1.6 Radio
80 0.6 Radio
80; 0.15 Radio
0C5 0.5 Radio. IR
CS: 0.2 UV. radio
HZCS 0.02 Radio
32 0.005 UV

Abundancu: are given by number relalive to water. Table adapted

from CIOVLsel'. J. I998. Faraday Discussions. 109. 317.

from asteroids and comets. Direct evidence for interSIellar grains entering the solar
system has been found by dust particle detectors on space probes such as Ulysses
and Galileo. These detectors are able to measure the mass, speed. and direction
of incoming grains, and therefore are able to infer the grain sizes by assuming a
shape and density. At the end of the twentieth century. it has also become feasible
to collect samples of interplanetary dust by high-flying aircraft or spacecraft. The
390 The Origin aflmerrrei'lar Dust

Table [3.2
Chemical composition of Comet Halley

Dust Volatiles

lnorganics W'rth oxygen Hydrocarbons

22.7% silicates 44.0% H20 0.8% C1H2

2.6% R5 rroilire 2.5% HCOOH 0.3% CH4
[3% C graphite 2.2% HZCO 01% CJH2
0.4% S sulfur 2.0% CO; —-
2.4% H20 0.8% CO —

Organics Wrth nitrogen Sulfur compounds

7.0% unsat. hydrocarbons 1.5% N; 0.04% H15

2.3% with oxygen 0.6% HCN 0.03% CS;
2.0% with nitrogen 0.4% NH3 0.03% 5;
OJ % with sulfur 0.4% N2H1 —
2.4% water 0.2% C. H4N1 -

From Delsemrm. AH. 1998, in The Molecular Origin oferr. ed. A. Brock. 13. mo.

collected l'DPs are found to have sizes of 5—20 Jtrrn and weigh about I nanogram. The
laboratory mass spectroscopic and isotopic analysis of the samples makes possible
the determination of their extraterrestrial origin through the detection of isotopic
anomalies. While the most common ingredient of interplanetary dust is silicates. the
carbonaceous material with both aromatic and aliphatic hydrocarbons is also present.
Specifically. the 3.4-,um feature of aliphatic C—H stretch seen in planetary nebulae
(Fig. [2. l0) and meteorites (Fig. 13.7) is also seen in the spectrum of interplanetary
dust. Various organic functional groups have also been identified with the C. N. and
0 X-ray absorption near-edge structure (XANES) technique.

13.5.3 Planetary Atmospheres and Surfaces

Organic molecules are commonly found in the atmospheres of the planets Jupiter.
Saturn. Uranus. Neptune, and Pluto. as well as satellites such as Titan and Triton.
In addition to water ice. frozen hydrocarbons are also believed to be present in
the icy surfaces of many planetary satellites, including Triton. Ganymede. Callisto.
and so forth. There is no doubt that gas-phase chernisu'y is ongoing in planetary
atmospheres. and the surface ice chemisu'y may have been aided by solar UV. cosmic
rays. and magnetospheric particles. Furthermore. laboratory simulations have shown
that reactions of methane and ammonia subjected to high-energy sources can yield-a
dark organic solid called tholins. Liquid HCN in the presence of amine and ammonla
 l3.5 Interstellar Dust and the Solar System 391

IIITTI1_I_I_IIIT_I'_IIIIllifIIjI‘lllllll‘Tlllllll'

Flux density (1043 W tn 1 gm“)

3.2 3.25 3.3 3.35 3.4 3.45 3.5 3.55 3.6

Wavelength (urn)

Figure 13.6
The United Kingdom Infrared Telescope { UKIRTJ spectrum of Comet PISwifi—‘lht'lle showing
broad emission features at 3.43 and 3.52 |urn. (a) The spectrum of the comet (data points)
and the modelled contribution from methanol (solid line). (b) The residual spectrum after the
subtraction of the methanol contribution. (From DaVies er al. I993. MNRAS. 265. 1022.)

can also polymerize to dark brown or black solid. The existence of such organic solids
can be inferred from the low UV reflectance of these planetary satellite surfaces.
The possible role that these organic solids may play in the synthesis of proteins and
nucleotides on planetary surfaces is a topic of fascinating speculation.

13.5.4 Meteorite:
Meteorites are commonly classified into three categories: stones. irons, and stony-
irons. Some stone meteorites are called chandrites for containing round millimeter-
size inclusions (called chondrules) distributed throughout the stone. Chondrules are
primarily made up of silicate minerals, the most common constituents being olivine
(forsten'te MgISiO... fayalite Fe28i04). pyroxene (enstatite MgSi03. fenosilite
FeSi03. wollastonite CaSiOJ. diopside CaMgSi205. hedenbergite CaFeSi205).
pyrrhotite (Fel_,S). and feldspar (albite NaAISigos. anorthite CaAIZSizos. ortho-
clase KAlSiJOg) (see Section “2.2). Of particular interest is the class of carbona-
ceous chondn'tes that contain a relatively high content of carbon and refractory
elements. Carbonaceous chondrites are believed to be fanned within a few million
years of the collapse of the solar nebula. and therefore are the most primitive of all
392 The Origin oflnrersrellar Dusr

Frequency (cm")
3050 3000 2950 2900 2350 2300
1 r l— l r I *—
o Galactic dust .-
Extragalactic dust ..
..... m... Meteoric dust

llllJlllllllJilllLlJJll
Optical depth

1.2 JIJJIIIIIILIIIIILIIlllllLillillll

3.25 3.3 3.35 3.4 3.45 3.5 3.55 3.6

Wavelength (pm)

Figure 13.7
The 136-. 342-, and 3.48-um aliphatic hydrocarbon features (cf. Table I 2.2] seen in the difl‘use
ISM (dots) and external galaxy (solid line) are also seen in the spectrum of the Murchison
meteorite (dashed line) (from Pendleton 1999. in Solid IntersrellarMarrer: The ISO Revolution.
Les Houches Workshop. February 2—6. I998. eds. L. d'l-lendecourt. C. loblin, and A. Jones.
EDP Sciences and Springer-Verlag. p. 120).

meteorites. Many meteorites, including the Murchison meteorite that fell in Aus-
tralia in I969, contain a large bulk of organic carbon in the form of a heterogeneous
strucrured macromolecular material similar to terrerstrial kerogen (Section 11.3.?)-
This material constitutes the dark matrix that binds chondrules and grains {033ml-
Enhanced deuterium abundances in these kerogen-like materials suggest that it is al
least partly interstellar in Origin. The soluble component of Murchison contains many
organic species. including aliphatic and aromatic hydrocarbons, alcohols. cmyl
compounds, amines. amides. and 92 amino acids. among which as many as 73 are of
extraterrestrial origin. The mereoritic amino acids generally have equal numbers 0f
left and right isomers. whereas amino acids of living things on Earth are entirelll left
 13.5 Interstellar Dust and the Solar System 393

Figure 13.8
Scanning electron microscope micrograph ofa 4-um pre-solar SiC crystal from the Murchison
meteOrite. The ”Ct”C ratio of this grain is 39. comparai to the solar ratio of 89, clearly
establishing that it is a pre-solar grain (picture from T. Bernatowicz).

isomers (Section 9.11). This suggests that molecules as complicated as amino acids
are synthesized beyond the Earth environment.
Molecules and grains of extrasolar origins have been found in carbonaceous
chondrites. Since most of the elements were homogenized in the early solar system,
the isotopic ratios of solar system objects are highly uniform. The discovery of nm- or
Jam—size dust grains in primitive meteorites with isotopic variations over several orders
of magnitude suggests that these are preserved pre-solar Stardust. The availability of
these materials in the laboratory allows the application of a variety of modern micro-
and nitric-analytical techniques that can reveal chemical and isowpic information with
the kind of precision impossible to achieve with remote astronomical observations.
Micron-size SiC grains have been found to have nonsolar '2c1’3c abundance
ratios and excesses of 7'2Ne. consistent with their being produced in carbon Stars
(Fig. 13.8). Because of the hardiness of SiC, they can be isolated in meteorites by
dissolving away everything else in harsh acids. Graphite. as well as nanodiamonds
with sizes of ~ 20 A {corresponding to a few hundred C atoms]. of pre-solar origin has
been found (Table I13). The su-uctures of the pre-solar SiC grains determined from
electron diffraction studies are found to be consistent with fi-SiC (Section | l.2.4).
Ion microprobe measurements show that they contain impurities such as Al. N. and
Ti. Preasolar graphite grains have either"caulillower“- or "onion"-like morphologies.
Pre-solar diamonds are found to be much more abundant than pre-solar SiC or
graphite, accouuting for ~ 6% of the total carbon in the Murchison meteorite. The
typical size of diamonds is between 1 and ID nm. and they are therefore referred
394 The Origin of Interstellar Dust

Table I13
Sizes and abundances of pie-solar grains in meteorites

Composition Diameter (Mm) Mum: (PP!!!)

Diamond 0.002 “no

Silicates (olivine. proxene. glass) 0.1-1 200
SiC (11-20 10
Graphite 1—20 10
11—. Fe—. 21—. Brio-carbides. Fe—Ni metal (101-02 ._
Si3N4 "' 0-31-I ~ 0.0113
Oxides (Al203. MgAl104, CaAanlg, 130;) (115-3 ~I

From LR. Nitller (private communication).

to as nanodiamonds (Section 13.3.3). Electron diffraction studies show that these

nanodjamonds are face-centered cubic crystals and are generally similar to ten'esu-ia]
macroscopic diamonds. While most nanodiamonds have solar 12Cl l3C ratios, the
presence of anomalous noble gas Xe suggims that at least some nanodiamonds are
pro-solar.
Since it is often necessary to dissolve the silicate "rnauix" of the chondrites in
order to isolate the pro-solar grains. much of the silicate material is destroyed in the
process. Consequently. pre-solar silicate grains were found in meteorites only in 2M4,
even though they are expec1ed to be more abundant than SiC. Pro—solar oxide grains
have been identified with ion imaging. Most of the oxides identified are corundum,
with a few being spinel grains (Section 1 1.2.3). The typical grain sizes are 0.3-5 um.
Also found by the ion imaging technique are pro-solar silicon nitride (Si3N4) grains.
Small grains of Ti—. Zr-, and Mo—rich carbides, kamaeite (Fe-Ni), cohenite ((Fe-Ni)C),
and metallic iron are also present in graphite grains. The abundances of these species
are much lower than pre-solar SiC grains (Table 13.3).
Isotopic measurements of light hydrocarbons (methane, butane, etc.) trapped in
carbonaceous chondrites have found them to be isotopically heavier (enriched in 2H.
|3C, and '5N) than their terrestrial counterparts, suggesting an extraterrestrial origin.
The 3.4-ttm aliphatic feature (Section 12.1.1) seen in circumstellar envelopes and
the ISM is also detected in meteorites by infrared spectroscopy (Fig. 13.7). X—ra)‘
absorption near spectroscopy at the carbon K edge (~ 290 eV) has identified various
functional groups. not unlike those found in protoplanetary nebulae (Section 12.“).
These results suggest an interstellar origin for the organic compounds in meteorites.
Evidence of primordial carbonaceous compounds can also be found in micro-
meteorites (~ 50—400 um in size) preserved in ice in Greenland and Antarctica Much
of the carbon in these micrometeorites is in the form of organic compounds. With an
accretion rate of ~ 20,000 tons per year. micrometeon'tes serve as useful laboratories
for the chemical connection between stars and the solar system.
 13.6 Possible Enrichment ofrhe Solar System by lnrersrellar Grains 395

13.6 Possible Enrichment of the Solar System by Interstellar Grains

There is ample evidence that organic compounds of aromatic and aliphatic structures
are made in circumstellar envelopes and ejected into the ISM. Laboratory studies also
suggest that amino acids and other complex organic compounds can be synthesized
in ice mantles of grains when irradiated by UV radiation. The presence of organic
compounds in carbonaceous meteorites also suggests that interstellar organic matter
can be preserved intact through the formation of the solar nebula and the accretion
of the parent bodies. However, it is unclear to what extent these organics contribute
to the origin of life on Earth. The possible role of pre-solar material in the biological
development on Earth depends on the following issues:

a Can these organic molecules and grains survive the journey through the ISM and
be incorporated in the solar nebula? To what degree do the interstellar diffuse
UV radiation field. cosmic rays, and shock waves contribute to the destruction
of these materials?
. Does physical and chemical processing in the molecular clouds (from which stars
are formed) significantly alter the chemical composition of these compounds?
Protostars are formed through the process of accretion. followed by the dispersal
of the parent molecular cloud by stellar outflows.
0 How much of the original interstellar material is eventually incorporated into
the circumstellar disk from which our planetary system emerged? The pro-solar
materials need to survive the initial accretion into the solar nebula. processing
in the nebula, and accretion to the planetary disk. If the accretiOn velocities are
too high. the grains may be vaporized. Collisions and sputtering could also alter
the grain composition. If the gas temperature of the solar nebula is too high. it
is conceivable that all the preexisting molecules and grains will be converted
to a well-mixed gas of simple atoms and molecules. Analysis of carbonaceous
meteorites provides the strongest evidence that interstellar organic matter is
preserved intact in meteorites through the formation of the solar system. Current
models of the solar nebula suggest that meteorites forrned about 3 AU from the
Sun at temperatures of a few hundred degrees. At such temperatures, it is quite
possible that interstellar grains can remain intact.
' To what extent does chemical processing alter the chemical composition of the
interstellar grains after accretion to planetary bodies? After the formation of
the solid bodies in the solar nebula. it is unclear how much further processing
occurred as a result of aqueous alteration and collisional impact. Our Earth is
believed to have been created as a result of accretion built up from a mixture of
early planetesimals. During this process. pre-solar material can be destroyed by
heating. shock waves, or chemical effects.
0 What role do comets play in the origin of life? Comets, which are created
in the outer solar system. are less affected by heating and are therefore more
likely to contain pre—solar material. The possibility that organic substances of
396 The Origin of Interstellar Dust

extraterrestrial origin can be delivered to planetary surfaces by comets has been

extensively discussed in the literature, but the effects on the origin of life fmm
such deliveries are not certain.

13.7 Summary

It is now widely recognized that solid-state compounds are an important part of

the interstellar medium. Micron— and submicren-size particles of both inorganic and
organic compositions are being made by evolved stars and ejected at high rates by
stellar winds. resulting in the chemical enrichment of the Galaxy. There is new
evidence that some of these grains survived their trips through the interstellar medium
and took part in the formation of the early solar system.
Through observations in the X—ray. UV. optical. infrared. and subrrun. chem-
stellar and interstellar grains can be studied in emission. scattering. absorption. In.
larization, and self-absorption of light. While some of the grains can be identified
as similar to terrestrial minerals through comparison between the astronomical spec-
tra and laboratory measurements. the presence of unidentified features suggess that
there exist compounds that are not found in the terrestrial environment. or at least
con-esponding to materials that are not yet well studied in the laboratory.
Recent advances in infrared spectroscopy have opened the possibility of the de-
tection of large, complex organic molecules and compounds with dozens or even
hundred of atoms. However. with the exception of simple molecules that show sharp
features. many of the observed infrared bands can be identified only with certain
chemical bonds or chemical groups, but not to specific molecules. This is because
many different molecules and compounds have similar chemical basic units. malt-
ing unambiguous identification of specific compounds from infrared specrroscopy
alone difficult. Recent developments in the identification of stellar dust material in
meteorites and interplanetary dust particles have aIIOWed the application of a vari-
ety of techniques to be used on the sample, therefore allowing a much more precise
determination of the physical and chemical properties of solid particles synthesized
in stars.
A
Chemical Reactions in the ISM
Tatsuhiko Hasegawa

Interstellar molecules are found in dark clouds. diffuse clouds. and circumstellar
envelopes. As of 2005, over 120 molecular Species. ranging from simple diatomic
molecules to unsaturated carbon chains to saturated organic species. have been de-
tected (Appendix 3). How these molecules come into being in the lSM is one of
the major challenges in modern astronomy. Since some of the detected molecular
species are not conunonly found on Earth. the study of interstellar chemistry can also
contribute to our fundamental understanding of chemistry.
Because of the low temperatures and densities of the ISM. molecules cannot
be formed from atoms by processes common in the terrestrial environment. New
chemical pathways (sequences of chemical reactions}, such as gas-phase reactions
involving molecular ions (Section 7.11), need to be invoked. Allematively. strong
shocks can heat and compress interstellar gas for a period long enough for chemical
reactions to proceed. Less understood. but believed to be important. is surface chem-
istry where molecular species are made on interstellar grains. By constructing the
chemical pathways and comparing the observed abundances ofinterstellar molecules
to those predicted from theory, we can impose constraints on the physical (radiative
and kinetic) conditions of interstellar and circumstellar environments. However. the
observed abundances of interstellar molecules do not necessarily result from chemical
equilibrium or steady-state conditions.

14.1 An Example: C0 Chemistry

The study of chemistry in space is still an evolving research field. A new laboratory
experiment could drastically change our understanding of specific chemical pathways
leading to a particular molecule. Also, a change in physical conditions usually results
in a significant change in the importance of individual reactions. As an illustration of
how molecules are formed in space. we will use C0 to discuss the various chemical
processes leading to the formation of this molecule. Detailed discussions of these
processes are given in the remaining sections of this chapter.
When exposed to the diffuse interstellarUV radiation field, molecules are usually
destroyed in less than 300 years. Molecules are. in tum. constantly formed from atoms

39?
398 Chemical Reactions in the ISM

C0 Formation Pathways In Diffuse Clouds

C hv
w R n gm..-
Figure 14.1
Chemical pathways leading to C0 in difiuse interstellar clouds. The dashed arrow represents
a radiative association reaction.

and atomic ions. However. unlike the radiative recombination of an atomic ion with
an electron. a merging process (called a radiative association reaction) such as H +
H -—> H: + flu or C + O -> C0 + hv in the gas phase is highly unlikely in space.
Instead, reactions leading to multiple products are much more efficient Examples of
such reactions are C + OH —-> C0 + H. C+ + OH —> CO“ + H. 0* + H; —> Ol-l+
+ H.
Let us consider a diffuse cloud with n" = 100 cm'3, T1. = 100 K. and AV =
l mag (from the cloud surface to the center). The first step of chemistry occurs
with hydrogen. The atomic hydrogen is converted to molecular hydrogen on grain
surfaces and the product is ejected into the gas (Section 14.3). In about 10J years.
n(H2)/n(H) reaches ID“. a steady-state abundance at n“ = 100 cm‘3 in a region
exposed to a diffuse interstellar UV radiation field. With the help of dust shieldinfl
and self-shielding against the diffuse interstellar UV radiation field (Section I43).
the molecular abundance rises beyond this value, and the central part of the diffuse
cloud becomes half H2 and half H in about 106 years. in this half-molecular gas.
CO is formed through a complicated sequence of reactions. Figure 14.1 is a gflPhjc
summary of the chemical pathways leading to C0 in the diffuse cloud.
 14.! An Example: C0 Chemistry 399

The ionization state of heavy elements in the diffuse ISM depends on the ioniza-
tion energy of the atoms in the ground state (Table A2. I). For the common elements
C. N. 0. and 5. they are likely to be in ionization states of C+. N. O. and 5+. Reactions
suchasC" +H2—) CH“ +H.0+Hz—)OH+H,andN+H1—>NH+H.even
though they have multiple products. do not occur in diffuse clouds because these are
endothermic reactions requiring extra energy (1'), > 400 K). There is no fast procem
that initiates chernisu'y in this environment. Instead. it takes slow processes working
over millions of years.
The hydrogen—oxygen chemistry is initiated by cosmic ray (CR) ionization of H
(Section 14.4).

H+CR—>H++e' +CR (RCR=Sx10"3s"). (14.1)

The reaction rate RCR has the unit of sec‘1 and includes the cosmic ray flux and
interaction cross section. This process takes about 0.7 x 106 years to ionize 0.0l% of
H or H2. The charge is transferred to O by

11+ + 0 —> H + 0+ (k = 7.0 x 10-'°e'232 1‘” cm3 s"). (14.2)

The production rate (R) for a gas-phase reaction has units of cm’3 sec". The rate
constant k is defined by R = r1 lnzk and has units of cm3 sec'1 for a two-body reaction.
in the reaction in eq. 14.2. n(H+) x n(0) x it gives the production rate of 0+. This
charge transfer process takes about 5 x IO4 years it“the oxygen abundance is l x 10“.
Once 0+ is generated. it is convened to OH or H20 in about a year through the
following reactions:

0+ + H; —> 0H"' + H (Hydrogen abstraction. k = 1.7 x 10‘9 cm3 s")

0H+ + 112 —> H20‘ i H (Hydrogen abstraction. k = 1.0 x 10-9 cm3 s")
H10+ + H; —> l-130+ -l> H (Hydrogen abstraction. k = 8.3 x 10"” ch s")
11,0+ + e— -> OH + H2 or 2H (t = 6.6 x aria/300 10—0-3 cm’ s“)
—> H20 +. H (Dissociative recombination.

k = 3.3 x 10-7(r/3oo Kr” cm3 s I). (14.3)

Separate from the hydrogen—oxygen chemistry. another slow process initiates the
hydrogen—carbon chemistry:

c" + H2 —> CH; + in; (k :40 x 10 “(r/300 rod/Sent3 5-1). (14.4)

This is called a radiative association reaction. This is one of the rare examples in
which an association reaction plays an important role in forming molecules in Space.
There is no alternative fast process to initiate the carbon chemistry at 100 K or lower.
If MHz) = 25 cm 3. it will take 3 x 106 years to convert all C+ to CH; through this
4“) Chemical Reactions in the ISM

reaction. However. once CH; is formed, the subsequent processes are fast with time
scales of about one year:

CH; + H2 —+ CH; + H (Hydrogen abstraction, t = 1.7 x 10-9 em! 3—1)

Ctr; + c —> CH + H2 or 2H (J: = 2.7 x refit/300 Kr”! em3 54)
—> CH2 + H (Dissociative recombination,

it = 7.3 x to-‘(r/Joo Kr”: cm] s“). (145)

Finally. energetically possible (exothermic) reactions of the products above, 0H
and on; with relatively abundant (3+. 0, and N, lead to co and CN. This step will
take about [04 years through the following reactions:

0‘ + OH —> co+ + H (Hydrogen ejection. t = 7.7 x 10‘'0 cm3 s"')

CO+ + H: —> HCO’r + H (Hydrogen abstraction, k = 1.8 x 10‘9 cm3 s")
CH; + 0 —> Hco+ + H2 (c. N, o condensation. k = 4.0 x 10“" cm3 5")
HCO"' + e' —> C0 + H (Dissociative recombination.

k = H x 1040,1300 K)—'em3s-‘). (14.6)

CN can be produced by similar reactions by replacing O with N in tire last two
reactions.
We should note that direct radiative recombination CO+ + e‘ does not yield
CO but C and O. A capture of an electron by a molecular ion usually results in a
breakup. hence the formation of CO requires HCO+ as a precursor. All products
above are constantly subjected to photodissociation. But the photodissociation time
scale is about 100—1000 years. so that only the end products C0. OH. H20. and so
on are affected. Molecular ions are quickly consumed by chemical reactions.
The preceding chemical pathways apply only to a narrow range of cloud con-
ditions. If the physical conditions change. some of the above-mentioned reactions
are taken over by other reactions. For example. if the difi'use cloud contracts to
n" = 1000 cm'3 and AV ~ 4.6 mag, the reduced radiation background will make
photodissociation negligible. Since H2 is constantly formed. most of the hydrogen
will eventually be in molecular form. The steady-state ratio will be ”(Hz) / n (H) ~ 103
from the balance of cosmic ray ionization of H2 and grain-surface formation of H2
without photodissociation. C+ will recombine in about 3000 years and become C.
Cosmic rays now interact mainly with H: to generate H+. which becomes H; (H3L
+ H; —> H; + H) (Section 8.2. I). H? is very reactive and is the prime driver in the
initiation of carbon and oxygen chemistry in diffuse clouds. For example, CH; and
OH+ are mainly formed by H; + C —+ CH+ + H2. followed by H; + CH+ —r CH; +
H. and H; + 0 -> Ol-l+ + H2. respectively. Without UV photons. C0 has only a few
slow destruction procasscs: C0 + H: -> HCO+ + H2. and C0 + He+ —* 0 + C"
+ He. Titus. CO accumulates to a point that most carbon nuclei are used up as CO-
 [4.2 Phorodt'ssociarian 401

The preceding example of the formation of C0 illustrates the uniqueness of

interstellar chemistry. The individual processes will be discussed in detail in the
following sections.

14.2 Photodissociation
Photodissociation refers to the breakup of a molecule as a result of absorbing a
photon. Unlike b—f photoionization of an atom (Chapter 4). molecules have negligibly
small absorption cross sections for a pure rotational—vibrational bound-free photo-
excitation within a ground electronic state. Thus. the photodissociation of a molecule
does not occur as a direct photo-excitation of vibration or rotation to the point of a
breakup tie, to the dissociation energy Do for the ground electronic stale)‘. Instead.
molecules have large photo-absorption cross sections for electronic (dipole permitted)
bwb transitions. and photodissociations occur through these electronic excitations.
The energy of an electronic excited state is usuaJIy significantly larger than Do.
In many (if not the majority) of the electronic excited states. a molecule is
still bound and stable. and the excited molecule may emit a photon and return to
the ground electronic state in a matter of IO 7 seconds without breaking up. The
large absorption cross section and the short radiative decay time are similar to those
in atomic transitions such as Lya in H 1. However. the absorption in an electronic
transition of a molecule occurs as a band mostly in the UV region centered at a
wavelength corresponding to the average energy difference between two electronic
states of the molecule. For an elecuonic transition of a molecule. the width of a band
is of the order of a few hundred A. A band spectrum actually consists of groups of
numerous narrow lines [the rotational—vibrational lines), where a group corresponds
to a particular set of vibrational quantum numbers of the upper and lower electronic
states. The interval of the groups is regular. In the 1000—2000 A region. it is difficult
to resolve and measure individual rotational—vibrational lines in the laboratory.
In many other electronic excited states. the electron distribution causes not a bind-
ing but a repulsive force between the constituent nuclei (a repulsive state). resulting
in a breakup of the molecule. In this type of phottxlissociation, individual lines in the
photo-absorption band are broadened or distorted due to the absence of the rotational—
vibralional levels in the upper electronic state and the very short lifetime (c I0"°
sec) of the repulsive state. The overall shape of the photo-absorption cross section
looks like a usual band measured at a low resolution (plus some overall distortion).
But the photo-absorption cross section in this case is intrinsically continuous. Pho-
todissociation of CH ‘, ON ’, and NH is believed to occur mostly through this type
of transition. This is illustrated in the schematic diagram shmvn in Figure 14.2a.

l. The dissociation energies Du given in Table A2.3 are for the ground electronic state ("0" in D0
stands for u = 0). It represents a minimum and is often insufficient for photodissociation However.
DD is important in collisional dissociation.
402 Chemical Reactions in the ISM

Energy

:-

U
+
(:0

Energy

(13)
Energy

A+B

(e)
Internucleat' distance

Figure 14.2
Schematic diagrams illusu'ating three different photodissociation processes. (Adapted from
van Dishoeck 1983. Rate Coefiicients in Astmchemistry. eds. T. J. Miller and D. A. Willem.
p. 209.)

In another type of photodissociation. a molecule is photo-excited to an electronic

excited state (a nuclear bound state). then. instead of retuming to the ground state.
the election configuration shifts to a third electronic state that is a repulsive stale
(Fig. 14.2b). The absorption band reflects the initial photo-excitation prams (elec-
tronic band transition with rotational-vibrational lines). but there could be significant
distonion or widening of the individual lines and of the overall band shape due ‘0
a short lifetime of the excited state. Photodissociation of CO and HCl is thought to
occur through this type of transition. Similar photodissociation processes occur in CH
and 0H.
 14.2 Phorodisrociarion 403

Another type of photodissociation occurs in H: where the molecule. at a certain

probability. decays frOm an excited electronic state to the ground electronic state with
a vibrational energy of nuclei beyond the dissociation energy. causing the molecule
to dissociate (Section 7.7.1). In this case. the initial photo-absorption process shows
no hint of a following dissociation. and the absorption cross section is intrinsically
discrete. reflecting individual rotational-vibrational lines in a band of an electronic
transition (Fig. 14.2c).
Most of the heavy molecules have many upper electronic states. Depend-
ing on which individual electronic state is excited. the outcome of the photo-
absorplion process can be quite varied, including possible repulsive dissociation.
bound—repulsive dissociatiOn. and nondissoeiation. For example. the CO molecule
has 48 absorption features involving 20 different electronic states in the 9| 2—1 152 A
region (each with widths of [~20 A) measured in the laboratory. Some of these transi-
tions lead to no dissociation. whereas others lead to [00% probability of dissociation.
The overall photodissociation cross section of a molecule is a superposition of the
many absorption features (some of which may consist of numerous discrete lines)
of a few to many electronic transitions that lead to a dissociation of the molecule. if
one or more electronic transition are identified. experimentally or theoretically, as
leading to photodissociation. then the photodissociation rate can be estimated.
As discussed above. the first step in photodissociation of a molecule is essentially
an electronic b—b transition. Analogous to atomic b—b absorption (eq. 5.45). the
absorption coefficient for the photo-excitation of a molecule can be written as

are 2
all z fji¢w (14-?)
mg:

where (by is not a simple Doppler profile function but an unspecified profile function
(but still normalized) for a UV band. 1f the probability of dissociation after UV
photoexcitation is denoted by p. the photodissociation rate (Rink in units of s‘ l) is
given by

R g
a 43 J'
_’
pd P h” .id 1’ . ( I43 )

The mean intensity J../hv in the integral in eq. l4.8 is a slowly varying function
of v. and can be approximated as a constant (Iv/ht!) over a molecular band. Since
f¢udv =1.

J, :tre2
de = 411(5) (mg) fjfp. (14.9)

Thus, once f1, (the band oscillator strength) is known. the problem becomes
tractable. The band oscillator strength is typically of the order of 0. [—0.1
For molecular hydrogen. the photodissociation occurs through an electronic
transition in the Lyman and Werner bands (Section 7.7.1). For the Lyman band
transition of molecular hydrogen. fj, = 0.28 (H; X E [u = 0. J = Oand l] —> 32 [all
v1). On average. about 23% of radiative decays from the excited state 3 8 occur with
404 Chemical Reactions in the ISM

an excess vibrational energy. resulting in a dissociation. The photon flux of the Habing
field (eq. 4.59) at 1000 A is 2 x 10 3 cut-1 5 1 Hz". Substituting these values into
cq. 14.11, we have R = 3.4 x 10- " Sec 1. When exposed to the interstellar radiation
field. molecular hydrogen is dissociated in less than [000 yr.
For C0. f11- = 0.24. This is a sum of band oscillator strengths of about [Weary
electronic transitions between 912 and 1152131 (co x: [u = o, J = o, 1, etc] _,
all possible electronic states [all vuPI). Nearly all of the upper electronic states result
in dissociation. so that p = l. The time scale thus calculated for photodissociation of
C0 under tlle Habing radiation field at 1000 A is 250 yr.
Photoiom‘zarion of a molecule refers to the removal of a bound electron upon
absorption of a photon. This can result in a molecular ion (XY + ltv —> Xy+ + 3—) or
in a dissociation of the ion into two fragments (XY + hu —> W“ + Y + e“). The latter
process is referred to as dissociative photoiont'zatt'on. Under the average interstellar
radiation field, molecular ionization rates are typically about 10"“ — 10"” sec-1,
and they are about ”10—1/3 of photodissociation rates of the same species. Given
below are some examples comparing the photoionization (Rpi) and photodissociation
(RN) rates under typical, unshielded interstellar conditions:

H20+hv—>H20'+e‘ Rpi=3.3xl0 ”5—1 (14.10)

H20+hv-+OH+H de=6.7xlD"°s" (14.11)

NH3+hv—>NH;+e Rpr=2.8x10"°s ' (14.12)

NH3+hv—>NH2+H de=l.lx10‘9sl (14.13)

H2C0+hu—+H2CO*+e Rpl=4.7x10 "’s-1 (14.14)

112c0+1w—a»C0+21-lnrl-t2 RPd=l.Ox10‘9s' (14.15)
Because of the abundant interstellar atomic hydrogen and its absorption of UV
photons (Section 4.3). Lyman continuum photons are generally not available for
the photoiOnization of other atoms and molecules. Therefore, interstellar atoms and
molecules can be photoionized Only if their ionization potential is less than [3.6
eV. This condition excludes the possibility of photoiOnization of several common
molecules such as H2. CO. CN. and N1. Ionization potentials of common atoms and
molecules are given in Table A2.3.

14.3 Attenuation of the Radiation Field

It is clear from the photodissocialion rates that most molecules cannot survive in the
ISM if exposed to the interstellar radiation field. The reason why molecules such as
C0 are widely observed in the Galaxy is that they are protected by interstellar dust.
which absorbs or scatters the UV radiation. From eq. 10.19. the decrease in UV flu!
 [4.3 Attenuation of the Radiation Field 405

as a function of AV is e QUVAV-"I'OMQV. For most of the molecules. photodissociation

occurs between 1000 and 2000 A. where the dust extinction efficiency ratio qu/ Q v
has a value of ~ 2.5. Therefore for each magnitude of visual extinction. the UV flux
decreases by ~ 90%. and the lifetime of the moleCules will increase by over a factor
of ID.
The detection of molecular gas adjacent to galactic H I] regions suggests that.
in addition to the ionization boundary due to the H II to H 1 transition. there also
exists a photodt‘ssociatt‘on region (FDR) where H; is decomposed into H atoms by
interactions with UV photons. Well-studied PDRs in the ISM include the Orion bar,
M17SW. 5140. and NGC 7023. UV photons longward of 912 A can escape from
the H I: region. so that UV photons at the discrete H2 line wavelengths between
9l2 and 18-44 A efficiently destroy H1. Therefore, the PDR. in which the transition
from H I to H2 occurs, lies between the ionization front and the molecular region. A
photodiSSoeiation front is geometrically very thin.just like an ionization front.
Although the vibrational dissociation energy of H2 in its ground electronic state is
4.43 eV (2770 A). the photo-absorption cross section for the pure vibrational bound—
free process without electronic excitation is negligibly small. Photons in the 2770—
l344 A band do not interact with or dissociate H2. even though they have energies
larger than the dissociation threshold of H2.
The phrase "photons at discrete line wavelengths" needs further discussion here.
H; has about 22.000 absorption lines between 345 and [84-4 A. of which about
500 lines between 9l2 and 1200 A (mostly originating from the v :0 state of the
grOund electronic state) are Strong (and destrucrive to H2). The absorption profile
for each ti2 line has a line width (FWHM) from 1.5 km s" (or 0.005 5. due to
thermal Doppler broadening at 100 K) to ID km s“l (or 0.033 A due to dynamical
broadening). so that l to 5% of the continuum photons between 9|2 and 1200 it
interact with H3. Since H1 is abundant, the H2 dissociating line photons are efficiently
absorbed at the surface of a molecular region. The optical depths at the center of
the strong H; lines reach unity even with hydrogen column density (N (H2)) as low
as 2 x l0"“l5 cm 2. In comparison. the visual extinction in molecular clouds is
Avtmag) ~ 1.2 x 10*“N(H2)(cm‘2) (eq. 10.21). which is much smaller than the
optical depth in the H; line. H: inside a molecular region is therefore protected by
H; near the surface of the molecular region even without dust attenuation. This effect
is called self-shielding. Some H2 UV lines are so saturated that observed absorption
spectra show widths as wide as l—5 A.
UV continuum photons not matching the H2 line wavelengths do not interact
with H2. so that they go deeper into a molecular region. where the only attenuation is
dust extinction.
For most of the other interstellar molecules. the overall profile of the photodis-
sociation cross section (either continuous or discrete) is spread over a few hundred
A in the UV region. Some bands extending into the [200—30003 region. The UV
continuum photons between the discrete H2 lines reach inside a molecular region (as
long as AV < l mag) and phOtodissociate heavy molecules in regions where H: is
entirely molecular. NH; and HZCO, for example, are easily photodissociated and are
found only in regions of heavy dust attenuation.
406 Chemical Reactions in the ISM

I n via'cn 37W 6's} 3i: 1'0 Ill l12 :5 {HARE I

I '(‘L I T r t I T l

' 0‘0

0 l-

[17.53.4115 9'75 3'1: To I'l— l: 73

7
g
E
.5

g l 71'7an an'in 3% ch si‘ lb u‘i IF ii IEISfiSB 1'sc 1%

'E
g .

a; v- | I :i CO

0 i—

915 920 93 930 935

Wavalength (A)

Figure 14.3
A synthetic spectrum showing the absorption bands of H3. l2C0. I3C0. and C130. A number of C0
bands coincide with the strong H2 bands and are therefore shielded from photodissociation. Some of
the I3C0 and C'RO bands are shifted from the CO positions and therefore do not benefit from cross
shielding (from Warin el‘ al. I996. AM. 308. 535).

One important exception is C0. C0 has about 40 absorbing bands in the 912-
1150 A region. individual bands having widlhs of 1-10 A? The photo-absorption
cross sections are large in the bands. Many of the bands are intrinsically continu-
ous in absorption cross sections, while other bands consist of numerous rotational
lines. Through these absorption bands. CO can be photo-excited to one of the upper
electronic states, and undergoes dissociation by fast transitions to a dissociation state.
However, by Coincidence. many of these C0 UV bands have wavelengths very
close to some of the strong H2 lines (Fig. 14.3). As the UV photons at the H2 “1“

2. About 3000 rotational-vibrational lines from 45 electronic u'ansiu'ons (bands) of CO hm: hm

identified in the 9130—1 ISO A region. The interval between rotational-vibrational lines in a band It
extremely narrow, and each band is only as broad as an H2 line.
 14.5 Gas-Phase Reactions 407

wavelengths are absorbed by H; at the surface of a molecular region. the photodisso-

ciation rate of C0 is greatly reduced even without dust extinction. This phenomenon
is called mutual shielding or cross shieiding.

14.4 Cosmic Ray Ionization

Atoms and molecules in space are subjected to a low- level flux of high-energy charged
particles (cosmic rays) with energies in the MeV and GeV range. These particles are
protons. a-particles. and nuclei of heavy atoms. The interaction cross section of H2
(or H) with high-energy particles is relatively small and varies inversely with energy.
Experiments are fitted by the following formula near 1 MeV:

emu!2 + CR) = 3.5 x 10 "7(ECR/MeV)'°'9 cmz. (14.16)

Low-energy (1 MeV < E < l GeV) cosmic rays are the most important in
ionizing gas in both diffuse and dense clouds. Cosmic ray fluxes are observed on
Earth for E > I GeV. but cannot be reliably measured for E < 1 GeV. Based on
extrapolation from the (Self data and other constraints, the intensity of cosmic rays.
I (E). in the Z-MeV to l-GeV region is estimated as I (E) ~ 0.1—] (proton cm“2 soc ‘
sterad 1 GeV").
When a high-energy particle ionizes an atom or molecule. the ejected electron
has an energy higher than l3.6 eV. The effect of secondary ionization by the ejected
electron is included in the following estimates of cosmic ray ionization rates:

H+CR-aH° +e—+CR ch~6.0x10"as" (14.17)

H2 +CR —> H; +e‘ +CR RCR ~ 1.2 x 10 ”s“ (14.13)
H2+CR-> H+H+CR RCR~1.3>< 10-133“1 (14.19)
H2 + CR ... H + W + e" + CR itCR ~ 2.2 x 10-19 s" (14.20)
He+CR—> He++e' +CR Rca~6.5x 104%“. (14.21)
Notice that cosmic rays mainly ionize H2 rather than dissociate it into neutral H. Yet.
H; quickly reacts with abundantly available H2: H2+ + H; —> H? + H. Thus, the
result of cosmic ray ionization of H2 is still production of H. These estimates are still
subject to revision. and some caution should be taken in their use.
A cosmic ray particle loses only a small fraction of its energy in one ionization,
and reaches deep into dense and heavily obscured regions (up to AV ~ 100 mag).
Cosmic ray ionization is an important process in ionizing the gas and initiating
chemistry in the dense clouds shielded from the interstellar radiation.

14.5 Gas-Phase Reactions

Although interstellar molecules are readily destroyed by photodissociation at low A”,

the destruction may be balanced by a number of formation processes. In this section.
408 Chemical Reactions in the ISM

we will describe some of the chemical processes that occur in the gas phase. In general
the gas density under interstellar conditions is so low that multiparticle gas-pm;
chemical reactions are unlikely. and biparticle reactions are the major process that
forms molecules in the gas phase. In a biparticle gas-phase chemical reaction, two
atoms or molecules encounter and their electron clouds come into contact. Such an
encounter is called a hard collision. The reaction partners form a temporary Complex
and then depart as dilferent species. A merger into a single species (an association
reaction) is possible. but the probability is low in interstellar clouds.
Actually. a hard collision does not necessarily lead to a chemical reaction (new
products). The original collision panners may just depart intact except for aneachange
of translational kinetic energies and momenta (an elastic collision). Alternatively.
t'ney may depart chemically intact but with different internal excitation energies (an
inelastic collision or a collisional excitation). We first discuss the rate of encounters
between an ion and a neutral gas particle. then encounters between neutral gas
particles. The rate of chemical reactions is the product of the rate of collisions and
the probability of the reaction resulting in new products.

14.5.1 Ion-Neutral Collisions

When a neutral particle is close to a charged particle. the neutral particle becomes
an electric dipole induced by the electric field of the charged particle. and causes an
attractive force between the two. The interaction potential between an ion of charge it
and the induced dipole moment (p. Section 5.6) of a neutral particle can be written as

2
He
vm = _ (T) 7-4. (14.22)
where a (defined by p = aE) is the polarizability of the neutral particle and r is the
separation between the two particles. Typical values for or are 0.667 x 10‘ 2“ cm3 for
H. 0.77 x 10-“ cm3 for 0.0.79 x104“ at? for H2. and 1.13 x 10-14 cm3 for N2.
In order for a hard collision to occur, the two particles have to pass each other within
the critical impact parameter

2 134

be = (flu—e5) . (14.23)
p.11

where u is the reduced mass and u is the relative velocity at large separations. The
critical impact parameter is derived from the condition that an incident particle with
an impact parameter b0 settles into a circular orbit. If the impact parameter is less
than on. the incident particle spirals to the center of mass clue to the steep potential
field. resulting in a hard collision. The cross section for hard collisions is givcn by
0(1)) = abs. Assuming a Maxwellian velocity distribution f(u. T) (eq. 2.37). we see
that the rate coefficient is given by

lt =fa(v)vf(v. T)dv

= 271(an/u) ”2. (14.24)

 [4.5 Gas-Phase Reactions 409

It is interesting to note that It is independent of temperature for ion—neutral encounters.

Although the frequency of collisions is higher at high temperatures. this is balanced
by a smaller value of £70 at high velocities. Typical values of k are ~ 10‘9 ch s‘].

14.5.2 Neutral—Neutral Collisions

Neutral particles interact as a result of mutually induced dipoles in the reactants. A
neutral molecule. even a nonpolar molecule. has an instantaneous dipole moment
at any moment. Such an instantaneous dipole induces a dipole in a second neutral
molecule. The induced dipole interacts with the first dipole. The interaction potential.
known as the van der Waals potential (sometimes also refen'ed to as the dispersion
term), is given by

V(r) ~ —aAaBlr—6, ([425)

where I is the ionization potential (more precisely. I = 1,. Ila/(IA + 15)). This is often
the most dominant long-range potential between neuu'al molecules. Olliet possible
interaction potentials are ignored in eq. 14.25.
The corresponding critical impact parameter and rate coefficient are

U3 1/6
b0: (3) (691%)
in)
(14.26)
2/3 [13 IN
k-en (2) (E) (E) _ (I427)
2 #- .u
The critical impact parameter is derived from the same condition as in the ion-neutral
case.
For neutral—neutral encounters. k has a weak temperature dependence. For H + O.
l =13.6BV,IIH = 0.667 x 10-24 cm3.ao = 0.77 x 10-14 cm3. p. = (ls/17m“. and
Hi! + 0) = 3.4 x lO"°T'/" cm3 s-'. This value ofk(H + 0) for hard collisions is
about a factor of 10 larger than experimental results. In some cases. the preceding
approximate formula gives predictions close to experimental values (see Section
14.5.5). Representative values are about 10'” — l0"° cm3 s" for neutral—neutral
hard collisions.

14.5.3 Exit Processes

The encounter of two particles A and B results in a molecule in an intermediate.
excited state (A B)‘, which can decay in several ways. These are often referred to as
exit channels. Possible exit channels include

0 return to the initial state,

A+B—> (AB)‘ —> A+B; (14.28)

410 Chemical Reactions in rhe ISM

- form a new molecule by radiative association.

A+ 13-» (AB)"’-+ AB+hu; (14.29)

- undergo a three-body reaction,

A+B—> (AB)'+M-—>AB+M. (1430)

where a third panicle M carries away the excess energy.

In contrast to the terrestrial environment where three-body reactions are common, the
low densities of the ISM make three-body reactions almost entirely negligible.
These processes have the following approximate reaction rates:

t.(A +3) = 1 x 10-10 cm3s"'.

k2(AB' -> A + a) = I x 10" s".
k3(AB" —» AB +13») = 1 it 10‘s".
k4(AB"+M) = 1 x 10"”em3s"'. (14.31)
The rate constant for each branch is given by the product of the initial encounter rate
(In) times the branching ratio Iii/[k2 + k3 + k4n(MJ]. For radiative association, it ~
hag/k2 ~ 10- '0 x 10+B/10'4 = 10‘ '6 em3 5' '. An example of radiative association
is C+ + H; —> CH; + hv. which has a theoretical reaction rate of k = 4.0 x
10"5(T/300 K) ”5 cm’ s". The rate for a three-body reaction (~ klk4n(M)/k2)
is larger than that fer a radiative association reaction only in our atmosphere with
MM) ~23 x 10'9 cm‘3 (the Liosehmidt number).3 It can also be seen that most
collisions in this two-atom case will result in no reaction (k2 channel).
Now. if at least one of the reactants is a molecule AX, then there can be other eitit
channels k5(AXB' -+ AB «'- X). k6(AXB" -> A + BX). and so forth. with excess
energy being carried away as translational h'netic energies of the products. Here.
It; through h in eq. 14.31 should be read as: k.(AX + B). k2(AXB' -—> AX + B).
k3(AXB‘ —> AXB + hv), k4(AXB' + M). lfthe exit channels ofthe new products
are energetically possible and conforming to other reaction rules (spin conservation.
etc.). the rates for these multiple product channels can be as large as kg, and the
reaction probability for new products upon a collision can be close to unity. Unless
measured in the laboratory. it is alien difficult to predict which product channel is
likely to occur.

3. The Loschmidt number is the number density of ideal gas (N0 = PD/kl'o) at standard :1me
(P0 = 1013st g cm" 5'1) and 0° Celsius (To = 273 K).
 14.5 Gas-Phase Reactions 41]

14.5.4 Ion—Molecule Reactions

If A+ + BC -> AB' + C (instead of —> ABC“) is energetically possible (i.e., exother-
mic). the formation energy can be carried away as translational kinetic energies of the
products. This will greatly increase the probability for the reaction to occur after a
hard collision. Many reactions of the type

A++BC—> 1413+ +c (14.32)

are known to Occur at near-unity efficiency upon a hard collision. Typical values of
rate constants for ion-molecule reactions are about I x 10‘ 9 cm3 s‘ '. very close to the
encounter late predicted in Section [4.5.1. Laboratory experiments demonstrate that
many ion—molecule reactions have no temperature dependence over a wide range of
temperatures (300—1000 K). consistent with the general prediction we saw in Section
14.5.1. Thus. 300-K rates are often used as IO-K rates in astrophysical applications
without a temperature con'ection. These reactions have a weak species dependence
mainly through the polarizabiliry.
Examples of ion-molecule reactions include

- proton transfer reactions.

H; +C -—> CH+ +H2 k = 2.0 x10‘9 cm! s"1

H; + 0 —> OH+ + H; k = 8.0 x [040ch s"1

011+ + N2 —» N2H+ + o k = 3.6 x 10"ocm3 s“. (14.33)

- hydrogen atom abstraction.

0++H2—>OH++H k=l.7x10'9cm3s". (14.34)

0 hydrogen atom ejection.

c+ + H20 —> Hco+ + H k = 9.0 x 10"0 cm3s-', (14.35)

. heavy atom condensation,

0* + cm; —> C211; + H k = 1.1 x 10'9cm3s"

—> (21,11;r + 112 k = 0.4 3-110—9ch s“,
and

' charge transfer.

o++H—.0+H* i=7.0x1o"°cm3s'
co++CH4—>co+CI-1; i=3.9x10"°cm3s"
N; + HCN -, 1.12 + HCN+ k = 3.9 x 10-"J cm3 5". (14.36)
412 Chemical Reactions in the ISM

ion-molecule reactions have proved to be successful in explaining lhe abundance

of many molecular species, in particular in diffuse and translucent clouds.

14.5.5 Neutral-Neutral Reactions (Multiple Products)

Some reactions are ltnown to occur at near-unity efficiency upon a hard collisitm
between neutral species (and the rates are close to the values estimated in Section
14.5.2). But in some other cases reactions do not occur at all. even though they are
exothermic. Many reactions have various temperature dependences that arise fiom
activation energies and endarhermiciries. Activation energies and endothenniciues
of the order of [00 K are not detected in experiments at room temperature, but can
dramatically reduce the reaction rate at interstellar temperatures on the order of to
K. Biparticle neutral reactions of simple radicals are now studied in the laboratory at
low temperatures. Below are some examples of neutral reactions.

N + CH _. CN + H k = t.66 x 10"°(T/300 Kr“ cm3 s"

O+CH —>C0+H 2:360 x i0””cm3s"
CN + NH; —> HCN + NH2 1: = 2.6 x lO'”(T/300 Kr“ cm33"
(2+02 —» co+o 1430010 = 3.3 x 10'”ch s"
N + CN —> N2 +C moo K) = 3.0 x IO‘IOcma s"
o + H2 —> OH + H k = 3.43 x l0‘”(T/300 K)2‘°7e_3]6°/T cm’ s-1
(14.3?)
The last reaction is endothermic by 900 K, but there is an additional energy barrier
of 2000 K.

14.5.6 Radiative Recombination

As in the case of H recombination (see Section 4.5). a free electron and an atomic ion
can recombine and emit a photon:

x3 + e‘ —+ x + hv. 04.33)

The radiative recombination coefficient k“ is defined such that kunmufi') gives

the number of recombinations per unit volume per second. Since :1, and n(X+) are
number densities. it“ has the units of cm3 s“. For example. singly ionized carbon
is widely present in the ISM (Fig. 5.l0), and will recombine to form neutral C when
free electrons are available:

C+ +e' —+C+hv. (14.39]

The accurate recombination rates for H+ (and a general theory for an accurate
calculation of the recombination rate) are given in Section 4.5. Given below are
approximate rates for radiative recombination for H+ and 0'. These analytic ‘5‘
pressions would be useful in getting an approximate idea about their temperflm
 14.6 A Role Equation 413

dependence and their values at low temperatures.

H+ + e- —> H + hv k r 3.5 x 10-”(r/3oo 10‘0” cm3 s"

C+ + e' —> C + hu k =4.4 x 10 ”(T/300 K) °-°1cm3s ' (14.40)

14.5.? Dissociative Recombination

Dissociative recombination occurs when a molecular ion rec0mbines with an electron
and breaks down into two simpler species. for example.

HCO++e' —>C0+H. 04.41)

The reaction rates for some examples of dissociative recombination are given
below.

1130* + e- —> OH + 2H k :65 x 10‘7(T/300 K) ”2 cm3 s 1

1130* + e- —> H20 + H k = 3.5 x l0‘7(T/300 K) W cm3 s 1
o; + e- -> o + o k = 2.0 x tut-707300 K)‘ “cm3 s 1 (14.42)
Comparisons between eqs. 14.40 and I4.42 suggest that dissociative recombina-
tion rates for molecules are about [CF—IO6 times larger than radiative recombination
rates for atoms. Therefore, radiative recombination of molecular ions (without disso-
ciation) plays a relatively minor role in interstellar chemistry.

14.6 A Rate Equation

The time variation of the density of species t' can be expressed in a general form of a
rate equation:

dnti) . . . . . .
dt —_n(r);n(y}k(i+y->l+m)—n(t)Z:R(t+huj—>l+m)
J

+ E Zn(i)n(m)k(l + m —> i + j) + Zntlmu + hv —> i + j).

I m l

(14.43)

The density (cm 3) of species 1' is denoted as nti). and rate constants are denoted as
k and R with a corresponding reaction in parentheses. 0n the right-hand side of the
equation, the first term is the loss of speciesi due to a reaction with species j at rate 1:
(cm‘ s' l). The second term is the loss of species i due to ionization and dissociation
by photons of type j at rate Rpi and RF! (5 1). where Rpi and Rad include the photon
flux and its attenuation. The second term also includes ionization and dissociation
by cosmic rays. The third term describes the formation of species i due to a reaction
between species I and m. The fourth term corresponds to the formation of i as a result
of dissociation or ionization of species 1 by photons or cosmic rays.
414 Chemical Reactions in the ISM

If the left-hand side of equation I443 is set to zero. the equation gives a Steady-
state abundance. In the simplest case, the steady-state abundance of H2 is calculated
frOm the following system of equations:

o = “$1” = —n(H2)R(H2 + hv) + 3......(H + H —> Hztnflntn)

nH =n{H) + 20(H2). (14.44)
where Rpm is the rate of formation of H: on grains (Section 14.8.2). Note that
an analogous expression for H (dntH)/dt = - - -) is redundant and that a particle
conservation equation is necessary to close the equation system in the steady—sun,
approximation. (In a time-dependent calculation, two equations for dn(H2)/dr and
dntH)/dt should be used, with the conservation equation being used only far a
consistency check.) The value for n" muSt be specified. and the photodissociation
rate includes attenuation.
In most cases. even if all reaction rates are known, the abundance of a molecular
species and the formation pathways leading to the molecule become known only after
an extensive calculation of many other relevant molecules. In order to carry out such
a calculation. the problem needs to be set up systematically.
First. the relevant elements should be specified. If one wants to know the C0
abundance. the relevant elements would be H. He, C. N. 0. and probably S or Si
(or a metallic element). Then. atomic. ionic. and molecular species (made of One or
more of the selected elements) need to be specified. The size of the set of molecular
species is determined empirically. A few dozen intermediate species that should be
considered in a modeling study of C0 are discussed in Section 14. I.
For each of the listed species. at least one formation process and at least one
destruction process should be considered in order to close the chemical reaction
network. The destruction products and the precursor species must be in the list
of Selected species. Ideally. several to a dozen reactions should be considered for
each species. After compiling a network of chemical reactions, one can calculate
the expected abundance of each chemical species using the rate equations. In a
steady-state approximation. not all the rate equations for all species are independent.
Equations for conservation of elements and charge should replace some of the rate
equations.
In addition to the reaction rates. we also need to specify the density of hydrogen
nuclei. the abundances of the relevant elements. the gas temperature. and the atten-
uation of radiation (usually AV) to complete a chemical model. All these variables
may also have spatial dependence. For example. in a l-D spherical case. they can be
functions of the radial distance r; in a plane-parallel case. functions of 2.

14.7 Photon-Dominated Regions

Molecular gas near or adjacent to an H II region or a reflection nebula is subjected
to UV radiation fields 102 to 105 times stronger than the diffuse interstellar radia-
tion field. The molecular envelope of a planetary nebula is also affected by Slmlla-l'
 [4.7 Photon-Dominated Regions 415

strong UV radiation fields from the hot central star. TheSe regiOns are called photon-
dominared regions (FDR's). PDR is also an acronym for a photodt'ssociatt'on region.
which is commonly used interchangeably with photon-dominated regions. In the
PDR. molecules are usually photodissociated on time scales of less titan one year.
Yet, intense molecular-line emission is observed in the PDR. Obviously. the observed
molecules are quickly and abundantly re-formed from amms and atomic ions that have
been released as a result of photodissociation of molecules. As an example of the
chemistry of PDRs. we consider a high-density, high-temperature region in a UV ra-
diation field. In spite of the higher photodissociation rates, high molecular abundances
are possible.
In a PDR, the gas is heated to about 1000 K by the intense UV radiation. Major
heating mechanisms are (l) photodissociation of H1; (2) collisional de-excitation of
H; from high rotational—vibrational levels where UV excitation lo (and nondissocia-
tive decays from) an excited electronic state is the excitation mechanism: (3) ejection
of photo-electrons from dust grains due to UV radiation; and (4) ionization of C and
other heavy atoms with ionization thresholds lower than 13.6 eV. The high tempera-
ture is an important condition to maintain high abundances of various molecules in the
PDR. Ordinary interstellar clouds (A v > 2—3 mag) are entirely molecular and rich in
molecular species at gas temperatures from ID to 20 K. But it takes millions of years
to reach such a full and rich molecular state at such temperatures, even under heavy
protection by dust from the diffuse interstellar radiatiOn field. In the PDR. observed
molecules must be rte-formed from atoms in a very short time. Gas temperatures on
the order of 1000 K enable endothermic reactions and rapid processing of molecules.
In the outer layers of PDRs. where the gas is mostly atomic. the principal species
are C". O. N. and H. When heavy molecules (CO. in particular) have been broken
down to atoms and atomic ions and 10—90% of H2 has been dissociated. the gas
initially contains mostly c+, N. 0. H. H2. and other metallic ions. The PDR chemistry
starts from these ingredients and rapidly builds up molecules. Molecular hydrogen
must be present at levels higher than a few percent. hOWever, to initiate the molecular
chemistry.
The characteristic chemistry in the PDR is initiated by endothermic reactions

0+Hz—r OH * H (endo by900Kplus E."l =2000 K) “4.45)

CI + H: -> CH‘ + H (endo by4640 K). (14.46)

where (endo) means endothermic. and E, is the activation energy. The products OH
and CH‘ react with abundantly available H2. 0". 0. and N to form simple molecules
characteristic of the PDR. For example, water is formed by

OH+H2-> H20+H (Ea: 1660 K). (14.47)

This reactiOn (exodtermic but requiring an activation energy) is responsible for the
high abundance (1(H10) ,— 2 x 10 '3) of H20. An important chemical indicator
(signature molecule) of a PDR is CO+. which is peculiarly abundant in the OriOn
bar and in the planetary nebula NGC 7027. C0 has an ionization energy of 14 eV
416 Chemical Reactions in the ISM

Figure 14.4
Chemical pathways leading toCN and HCN (top) and to C0‘-L and HCO+ (bottom) in photon-
dominated regions. A dashed arrow represents an endothermic reactiOn or a reaction with an
activation energy (from Hascgawa er «1'. 2000. ApJ. 532, 994).

(larger than 13.6 eV for H). so that CO+ cannot be produced by photoionization of
C0. Instead CO' is produced by chemical reactions from C+ by

OH + O” —> c0+ + H. (14.43)

C0+ then reacrs with H and H1 through the reactions

CO+ +H—r CO+H+

co+ + H2 —, Hco+ + H
1103* + e —> CO+ H (14-49)

to generate another signature species of the PDR. HCO+. A graphical summary Of

the C0+ and HCO' chemistry is given in Figure MA.
The formation orCH * (eq. 14.46) is followed by hydrogen abstraction reactions
and subsequent dissociative recombination reactions:
 14.7 Photon-Dominated Region: 41?

CH++H2—>Cl-I'2"+H
CH;+Hz—>CH;'+H
CH;+e"->C+H2
CH;+e'—>CH+H
CH;+e‘—>CH+21-1orH2
CH;r +e- —> CH2 +H. (14.50)
These simple hydrocarbons (and their protonated counterparts) react with N to form
CN+, HCN+. and HCNH+:
CH+ + N —> CN+ + H
CH;+N->HCN++H
CN+ + H2 —> HCN+ + H
HCN”r + H2 —» HCNH+ + H. (14.51)
The molecular ions either recombine dissociatively or transfer their charges to H to
form CN and HCN through reactions

HCN++e‘ —r CN+H
HCNH+ + e' —r HCN + H
CN+ + H —> CN + W
HCN+ + H —» HCN + W. (14.52)
CN and HCN are also fomted through neutral—neutral reactions

CH + N —+ CN + H
CH2 +- N _. HCN + H
CN +H2—> HCN+H (Ea='1'fio K). (14.53)

The lasr reaction (eq. I453) is exothermic by about 10,000 K, but has an activaIiOn
barrier Ea ofabout 760 K. This reaction accounts for 50 to 70% of HCN production.
The CNIHCN abundance ratio. therefore, tends to be higher at lower H2 concentra—
tions (or at lower temperatures). A graphical summary of the CN and HCN chemistry
is given in Figure 14.4.
Simple hydrocarbons are also important in initiating CS chemistry:

CH + s+ —> cs+ + H
cs+ + H; —> Hcs+ + 1-1
Hcs+ + e —> cs + H. (14.54)
418 Chemical Reactions in the ISM

The abundances of CH4. NH], SO, and SO; are predicted to be low bee-am of
the high photodissociation rates and the lack of an efficient formation channel. The
endothennicity is too high for reactions
Cu; + H1 —> CH: + H (endo. 31,000 K) (14.55)
N + ]-[2 —> NH + H (endo. 14.640 K)
(14.56)
NH + [-[2 —> NH: + H (endo. 3740 K)
([45?)
to occur efficiently. At high temperatures, the relatively high (more than 1%) alim-
dance of atomic hydrogen makes the reverse reactions of eqs. I455. 14.56, and 1457
efficient, hence contributing to die-hydrogenation of the hydrocarbons and nitrogen
hydrides. In addition. the high concenu-ation of electrons causes the destruction of
CH"+ and NH: ions prematurely through dissociative recombinations. preventing the
formation of saturated species CH4 and NH3. The abundance of HZCO is also pre-
dicted to be low because of photodissociation and destructive reactions with H and
C+ effective in the photon-dominated hot region:

1-12co + 1-1 —» HCO + H2 (endo. 1650 K) (14.53)

H200 + c+ —> CH;r + co (14.59)
HZCO + c+ —> Hc0+ + CH (14.50)
Hzco + c+ —> H2C0+ + c. (14.61)
The gas-phase chemistry in the PDR in a circumstellar envelope is therefore quite
different from a diffuse cloud away from strong heating sources.

14.8 Grain-Surface Chemistry

Gas-phase chemistry alone cannot account for the observed abundance of all molec-
ular species. For example, the most important molecule H2 cannot be made from two
H atoms in the ground state in the gas phase of the ISM. Many of the complex organic
molecules are also difficult to synthesize in the gas phase. It is likely that chemical
processes on the surface of grains play an important role in interstellar chemisty.
The hydrogen molecule has no electric-dipole moment and cannot quickly radiate
away the formation energy via vibrational or rotational dipole transitions even if mm
H atoms temporarily merge. Molecular hydrogen can therefore be efficiently formed
only in the presence of a third body with which itcan exchange energy and momentum.
For example, molecular hydrogen can be formed on grain surfaces where the excess
energy can be absorbed by the grain or can be consumed by ejecting the product.
In this scenario. gas-phase H atoms encounter and stick to the grains. Then. they
move around over the surface (migrate) and encounter (and react) with other surface
H atoms. The formation energy (4.48 eV) is partly absorbed by the grain. The newly
formed H2 is ejected from the surface. carrying away a significant fraction of the
formation energy as translational kinetic energy and internal excitation energy.
 [4.8 Grain—Sudan Chemistry 419

When a molecule encounters a grain. it likely sticks to the surface at a near-unity

probability at gas temperatures below 100 K. Even if the gas particle stays on the
surface for only 0.01 seconds, for example, this is a sufficiently leng time for various
surface processes. The energy can be exchanged between the adsorbed particle and
the surface in [0‘12 seconds. the time scale for the surface vibration- The particle
may circle around the grain many times during such a short time.
The accreted gas particle may (i) react with grain material or (ii) not react but stay
on the surface for some time. Colliding gas particles are predominantly (99.9%) H,
H1. and He. Therefore. any reactive grain surface is first subjected to reactions with
H atoms. particularly while dust grains are in diffuse clouds. Since He is chemically
inert, reactions involving He can be ignored. Since formation energies are likely
absorbed by the grain, almost all possible exothermic reactions with H would occur
to the grain material. Occasionally, an 0 or N atom may stick to the grainI but
frequently an-iving H atoms would likely react with the surface 0 or N atom first.
Thus. any reactive material or reactive surface would have been hydrogenated and
would have become chemically inactive by the time the environment of the grain
becomes that of a dense molecular cloud. At this point. the grain temperature drops
to 10 K, and the environment becomes predominantly molecular and opaque to UV
radiation. However. grain materials that are selectively reactive to heavy molecules
are not ruled out.

14.8.1 Adsorption and Evaporation

A molecule is adsorbed to a grain if it is bound to the grain Surface by van der Waals
force. The binding energy (adsorption energy or desorption energy). which is species
and surface dependent. is denoted as D. An adsorbed particle vibrates or oscillates in
the adsorption potential well at a frequency f0. 1ypical values of f0 are about 10'2 s‘ '.
although f0 has a weak dependence on species.
Since the adsorbed particle is not chemically tied to a molecule that constitutes
the solid surface. the adsorbed particle can evaporate from the surface under certain
conditions. The rate (per second) for classical thermal evaporation of an adsorbed
particle is given by

D
R"? = f0 exp[— EL (14.62)

where Ta, is the dust temperature and D is the adsorption energy. Equation 14.62 is
derived assuming that individual vibrations of an adsorbed particle are independent
events and obey the Boltzmann statistics in vibrational energy. The probability of
having a vibrational energy larger than D is the probability for the surface particle to
leave the surface in a vibration event. The adsorption energy (D/ it) is on the order of
50010 10,000 K. The inert He has 0/1: = [00 K. H has D/ft =350—450K. whereas H;
has D/k = 450—550 K. However, 0/1: for H2 drops to 100 K if the surface is coated
by a monolayer of H2 molecules. Current estimates of DH: are about BOO K for C,
N. and O atoms on an H20 ice surface. The relatively volatile CH4 has D/k = 1360
K on a graphite or silicate surface but Dl k = 2600 K on an H20 ice surface. C0 has
420 Chemical Reactions in the ISM

0/]: = 1740 K (H20 ice surface). 1200 K (graphite or silicate surface), and 960 K
(CO ice surface). H20 (accreted molecule) on an H20 ice surface has D [k = 5000
K. We can see from eq. 14.62 that the evaporation rate is sensitive to Td, With the
preceding values of adsorption energy, many volatile species (C0, CH4. N2. etc.) are
released into the gas phase in a short time if the dust is heated to 30 K.
Gas-phase molecules accrete onto grain surfaces on a time scale of 2 x 109mm,
yr. where y, = 0.1—1.0 is the sticking coeflicr’em. ln dark clouds such as the Tam-u;
Molecular Cloud. the gas and dust temperatures are both about 10 K. At this grain
temperature. molecular hydrogen evaporates from the surface in about a year. but
heavier molecules would not Lhennally evaporate within 1—10 million years at such
a low surface temperature. In comparison. at the density of n" = 10“ cm‘3_ the
accretion time is 105-”)6 yr. If thermal evaporation is the only mechanism to release
the heavy molecules from a grain surface. all heavy molecules (including C0) should
disappear from the gas phase in less than 1 million years. This prediction clearly
contradicts the observations. as many gas-phase molecules are seen in dark clouds.
This suggests that alternative desorption mechanism(s) must be at work. Possibilities
currently under study are mechanical desorption (grain-grain collision). chemical
desorption (formation energy). cosmic ray—induced desorption. and photodesorption.

14.8.2 Formation of Molecular Hydrogen on Grains

The formation rate (in cm3 s“) of molecular hydrogen from gas-phase H atoms
reacting on grain surfaces is traditionally expressed as Rsmina-l + H) x rt(H.l) x a".
where nH = n(HI) + Zn(H2) + n(H'). Assuming a sticking probability of l and a
reaction efficiency of l. we can write the rate coefficient as

Rmnttr + H) = 221““! (00-1)) cm3s-'. (14.63)

"H
where (u(H)) is the average thermal velocity of H atoms in the gas phase. The 1/2
factor accounts for the fact that two H atoms leave as one 1-]; molecule. Details of
what happens on a grain surface are ignored in the expression above. and all H
atoms that encounter grains are assumed to leave the surface as H2. If we assume
(utH)) = 1.57 ltms‘l (If,r = IOO K). a - 0.1 pm. (I; = 3 x 10 3 (dust mass to Hgas
mass ratio. Section 10.2). and p, = l g cm 3. then R51..."1 = 3.0 x l0 '7 cm3 s". This
level of H2 formation rate is consistent with observed Hz to H 1 ratios in diffuse
interstellar clouds. However, details of what actually happens on tile grain surfaces is
still the subject of active study.

14.8.3 Migration and Evaporation

In order to make the grain-surface chemistry at tractable problem. we here discuss
only an idealized case in which the grain surface is chemically inert and geometrically
smooth (like a clean crystal surface of quartz or graphite). _
An adsorbed molecule is trapped near the surface in a potential well. The potential
is a function of the displacement from the surface (measured normal to the surface)
 14.8 Gmin-Surfilce Chemistry 42]

W2)

3.
E
E-
8
'U
< —0.7D

o
Displacement from surface 1

Figure 14.5
Len: A schematic view of a solid surface (1 — y plane) with surface constituent molecules (dark
spheres). The displacement from the surface is 2. Three representative surface positions 1—3 are
indicated. Right: The adsorption potential is plotted as a function of displacement z from the surface.
The three curves labelled 1-3 are potentials at the three representative surface positions indicated in
the left panel.

at a fixed surface positiOn (measured along the surface), with the minimum of the
potential found slightly off the surface. The maximum depth of the potential is equal
to the desorption (or adsorption) energy D. The depth of the adsorption potential
varies with the position aIOng the surface. as depicted in Figure 14.5. This arises from
the nature of the adsorption potential. which is a superposition ofinteraction potentials
between the adsorbed particle and the individual molecules that form the surface.
Imagine a test particle that moves along the surface but with a censtant distance
from the average surface. The potential well is shallowest at the position right above
a surface constituent molecule and is deepest at the position above the midpoint of
surface constituent molecules. The depth of the potential well above the constituent
molecules is typically 50 to 70% of D (that of the deepest potential). The adsorbed
molecule naturally stays at the bottom of the deeper potential well.
For the adsorbed molecule to move around on the surface (to move to an adjacent
deep potential well). it must clear the shallower potential part. The difference in
depth between the deep and shallow potential wells is about 50 to 30% of D. and
this quantity, BB, is referred to as the potential barrier against surface migration.
The estimate of EB is dependent on the combination of the solid material and the
adsorbed particle, and different estimates exist. For the present discussion. we assume
E3 = 0.3D. When an adsorbed molecule clears this energy barrier. it is referred to as
422 Chemical Reactions in the ISM

having undergone a thermal hopping. The rate for thermal hopping can be estimated
with eq. 14.62. Since the threshold for ajump is now E3 instead of D for evaporation,
the expmsion for thermal hopping rate (hops per second) is obtained by replacing D
in eq. 14.62 with £3. The rate for thermal hopping must be used in conjunction with
the random walk statistics on a two-dimensional plane to estimate the rate of migratio"
(or the rate of diffusion) of the adsorbed particle. The average diffusion distance in
Nhop hops per second is Al ‘ [th where A! is the average distance between the sites
of deep potential. In practice. A! is the average separation between surface constituent
molecules. The area diffusion rate (cm2 s' l) is given by AFN”. By dividing the m
diffusion rate by the surface area of a grain. the rate for a surface molecule to sweep
Over the entire surface of a grain is

Rsweep -
— £51.13
411,02 (swee P s 5") - (14.64)

Forenample. for rd = 10 K,4rraz,/Al2 =1 x [05.and E,/t=o.3o/t =10“,

the thermal hopping rate for H atoms is 1.4 x if)3 hops 5‘1, and the thermal SWeeping
rate is 1.4 x [01 sweeps s".
The absolute value of the sweeping rate is sensitive to assumed (but often mm.
tain) parameter values. so that these values are only reliable to an order of magnitude,
However, a comparison of sweeping rates gives us some insight into what may hap-
pen to the adsorbed molecules and atoms. The ratio of sweeping rates for H and 0 is
expll40/Td], where EB(H)/k = IOO K and EB(O)/k = 240 K have been assumed.
The sweeping rate ofH is largerthan that ofObyafactor 1.2 x 105 (l0K)to 1.5 x 102
(28 K). The sweeping rate of H is about 100 sweeps s‘1 at Td = 10 K. Thus. an ad-
sorbed O atom will practically stay at one point on the grain surface at 10 K. whereas
an adsorbed H atom will circle a grain many times. In dense dark clouds. therefore.
heavy molecules will not move around on the surface of a grain. It is likely that they
will encounter surface H atoms many times (and react with H) before encountering
another adsorbed heavy molecule on the Surface.
An important consequence of this trend is that most adsorbed heavy atoms and
molecules will be hydrogenated. Possible examples of starting molecules and their
hydrogenated products are HCN —> CH3NH2'. C2H2 -r CZHE; and C0 -> CH30H
or HZCO. Also. C, N. and O atoms are likely to become CH4. NH3, and H10. in a
dense molecular cloud, the gas is mostly molecular. However. atomic H is always
present at a low level (n(H) ~ I cm 3 at any n (112)) due to a balance between cosmic
ray destruction of H2 (i.e., H generation) and grain-surface formation of H2 (i.e.. H
consumption). Combining with the immobility of the heavy molecules, the low-level
H is sufficient to hydrogenate the accreted molecules.
Although grain chemistry mainly concerns H because of its high mobility on
cold surfaces. diffusion of heavier species over the surface can become sisnjfi‘m'
at higher temperatures. Near a protestar or a young stellar object. the dust is often
heated to Ta. = 20 K. This modest change in Td dramatically narrows the EaP 1”
the surface sweeping rate between the heavy atoms and the atomic hydrogen. In
addition, the evaporation rate for H dramatically increases. resulting in a very 5'10“
 Famber Reading 413

residence time for H on a grain surface. The absolute value for the diFfUSion rates
of heavy atoms increases. so that heavy atoms become mobile, enabling the surface
encounter between heavy atoms. In such a situation, heavy complex molecules form
in abundance without hydrogenation. it has also been suggested that compounds of
high molecular weight can be produced on grains duough polymerization reactions
involving HZCO. NH3, and CH30H ice. The richness of the chemical composition can
be further enhanced if these ices are subjected to irradiation by interstellar diffuse UV
light (Section [3.4).

14.9 Summary

Molecules in the ISM interact with the diffuse stellar radiation field through photoion-
ization and pholodissocialion. The short time scale of photodissociation implies that
gas-phase molecules are constantly rc-fonned in the ISM. This is achieved through
a variety of biparticle gas-phase tactions including ion—molecule and neutral—neutral
reactions. or collisions with electrons through radiative recombination and dissocia-
tive recombination. The survival of the molecules can be considerably longer when
they are shielded from difi’usc UV light inside dense clouds. either through dust en-
tinction or self-shielding.
However. gas-phase chemistry alone is not sufficient to account for the observed
abundance of interstellar molecules. Molecules ranging from the simplest H; to
complex organics are synthesized on the surface of grains. Grain-surface chemisu‘y
therefore represents an important element of the radiation, gas, and dust interaction
network in the ISM.

Further Reading
Duley. W. W.. and Williams. D. A. 1934. lnterstellar Chemistry. Academic Press, London.
UK.
Watson. W. D. 1975. Atomic and Molecular Physics and the Interstellar Matter (Les
Houches Summer School Session XXVI). eds. R. Baiian. P. Emrenaz. l. Lequeux. North-
Holland Publishing Company, The Netherlands. p. l‘l'l.
Zangwill. A. 1988. Physics at Surfaces. Cambridge University Press.
Prunon. M. 1983.5udace Physics (2nd ed.). Oxford Physics Series. Oxford University
Puss (London. UK).
 15
Gas Dynamics, Gravitational
Collapse, and Stellar Winds

Gas motions in the ISM can be classified into three catagories: (i) random motion at
the microscopic level as a result of temperature: (ii) random motion over macroscopic
distances. such as turbulence observed in molecular clouds; and (iii) systematic
motion over large distances. such as gravitational collapse and stellar winds. Large-
scale systematic motions are initiated by either a continuous acting force. such as
gravity. or a sudden disturbance such as a supernova explosion. Except in relativistic
situations, systematic motion in the ISM can be described by Newtonian dynamics.
If the distance over which the systematic motion occurs is much larger than the mean
free paths of the random thermal motion of the particles. one can ignore the forces
acting on individual particles and approximate the systematic motion as that of afluid.
In such a case. we can employ macroscopic concepts such as density (p). velocity (u).
temperature (T), and pressure (P) to describe the properties of the fluid.
The systematic motion of a gas under the fluid approximation is governed by three
equations: conservation of mass. conservation of momentum (or under the action of a
forca. the equation of motion), and conservation of energy. If the gas has a finite
temperature. then it also possesses inlemal energy and pressure. If there exists a
pressure gradient across distance. the motion will result. even in the absence of a
force.

15.1 Hydrodynamical Equations

Consider an ensemble of gas of density p moving at a speed 0. From the conservation

of mass, any change in the density at a point in space must be balanced by the net
mass flux entering and leaving that point. The equation that governs the conservation
of mass is called the equation of continuity:

§£+v.(pv)=o. (15.1)
3:

425
426 Gas Dynamics, Gravitational Collapse. and Stellar “Ends

If this gas is subjected to an external mechanical force, then the acceleraficm of the
gas is governed by the equation of motion:

p [2; +01 . V)v:| = —VP — pv¢

. (15.2)

where P is the pressure and d: is the force potential. For example. in the presence of
a gravitational field. the gravitational potential is governed by

Vii" = 4" GP: (15.3)

where G is the gravitational constant. For a fluid of ionized gas in a magnetic field
B. the magnetic force term J x B (where J is the current density) would be added to
the right-hand side of eq. 15.2.
For a spherically symmetric system, the equations of continuity (eq. 15.1) and
motion (eq. 15.2) can be written in spherical coordinates as (Appendix 1)

3,0 l 3 2 _
5+7}; (r pv)—0 (15.4)
311 33 13_p
E v3r=—; ar' (15.5)

In one-dimensional rectangular coordinates where all the variables are functions

of x and: only. the corresponding equations are

3p tip 311
a:, +vax+pax
— — =0 .
(156)
a" + via—v
E 3.:
= —l——3P.
p 3.1:
(15.1)
In general. there is another equation governing the conservation of energy. bal-
ancing the change in kinetic energy. internal energy. and energy losses due to con-
duction. radiation. and so forth. For systematic motion in one dimension. the kinetic
energy per unit mass of the gas is :Lpuz. In a volume V containing number N of
randomly moving particles. the internal energy U is given by

U = "Yin/kn (15.3)

where :1! is the number of degrees of freedom. For random motion in three dimen-
sions. HI = 3. For an ideal (nonintcracting) gas,

P = N”, (15.9)
V
 15.1 Hydmdynantlcal Equations 42?

and therefore the intemal energy is

"f
U=3PV. (15.10)

From the first law of thennodynamics. the change in internal energy is equal to
the work done in compressing the gas:

dU=-PdV. (15.11)

Substituting eq. 15.10 into eq. 15.11, we have

filrpdv + VdP) = —PdV, (15.12)

which upon integration. gives

P o: v-“+2/~r>. (15.13)
The pressure therefore can be expressed as a function of density in this form:

P=KpV. (15.14)

where

y: l +2/nf. (15.15)

For a monoatomic gas with no internal degrees of freedom. :1 I = 3 and y has a

value of 5/3. For a diatomic molecular gas. which has two internal (rotational) degrees
of freedom. the value of y is 715' [n macroscopic thermodynamics. y can be shown to
be Cp/ C... where Cp and C“. are heat capacities under constant pressure and constant
volume. respectively. Equation 15.14 is called the equation afsrare.
If we define 1.1. as the intemal energy per unit mass. then from eq. 15.10. we have

= P (15.16)
(r—Dp'
In the derivation above. we have assumed that the system is closed. with com-
pression and expansion occun'ing with no exchange of heat with its surroundings.
This is referred to as the adiabatic appron'marian and y is called the adiabatic index.
If the time scale to achieve thermodynamic equilibrium as a result of heat exchange is
short in comparison to the dynamical time scale. then the temperature of the system
will be determined by the balance of heating and cooling:

l"(T)= A0“). (15.1?)

1. [f the diatomic molecule is not rigid. there is another degree of freedom due to stretching.
423 Gas Dynamics, Gravitational Collapse. and Stellar Winds

and can be considered a constant. This is referred to as the isothennal approximation.

In an isothermal gas, since T is constant. we have P o: p from the ideal gas law
(eq. 15.9). This implies that y in eq. 15.14 has a value of l. or 11f —> 00. Therefore the
isothermal approximation is formally equivalent to saying that during a Compressiom
the increase in internal energy is spread over so many internal degrees of freedom that
no increase in temperature results.
Let us consider a system of gaseous material that is initially attest ("o = 0) and
has density and pressure of pa and Po at x = 0 and t = 0. If this system is given
a perturbation at r = 0. changes in u. p. and P will propagate downstream (x > o)
with time (1 > 0). We can express these changes as
U=U0+IJI=U1

P=Po+101
P=Fo+ Pt- (15.13)
Assuming that the perturbations are small (p0 >> p1). we can substitute eq. 15.18 into
eqs. 15.6. 15.7, and 15.14. After discarding all second-order and higher terms, we
have. respectively.

n+3;
3 3
=0
at 321'
3111 l 3”] _ 0

at pg 31
P
P, = (y—U) p.. (15.19)
100

Differentiating the first and second equations in eq. 15.19 w.r.t. t and 1. respectively,
we obtain a linearized equation of motion:
2 2
§_pl-azifl_o
_ , 15.20
3:2 ° 3:2 ( )
where

ag=yfl. (15.21)
Po
We can recognize that eq. 15.20 is the wave equation and ac is generally known as
the sound speed.
For an ideal gas,

an = fl. (1522)
WH

As an example, we can calculate the sound Speed in the Earth‘s atmosphere. Since
the Earth's aUnosphere consists of primarily nitrogen and oxygen molecules (both are
 i 5.2 Seif-Gravitat‘ing Hydrostatic Sphere: 429

diatomic). ,u. = 28.3 and y = 7/5. For T = 273.15 K, on = 3.3 x 10'4 cm s". or 1200
km hr’ '. The corresponding sound speed in the neutral. atomic ISM is ~ 1 km 5".
assuming I" = 100 K. it = 1.3. and y = 5/3. While motions exceeding the sound
speed are rare in the terrwtriai environment. many physical motions (e.g.. stellar
winds) in the ISM have velocities greatIy exceeding the local sound speed.

15.2 Self-Gravitating Hydrostatic Spheres

Let us start our discussions on dynamics with a self-gravitating hydrostatic volume
of gas. In this case, the net force in every point is zero and there is no motion or
dependence on r. If we define the mass function M (r) as the total mass within the
radius r. then eq. 15.4 gives
dM(r)
= 4nr2p(r). (1523)
dr
If the only force present is gravity. then the gradient of the gas pregure at every point
must be balanced by gravity. 1n the static case. eq. 15.2 becomes

VP = —pV¢. 05.24)

In a spherical symmetric system where the only dependence is on r. eq. 15.3 becomes2

1 d
—-— —
2445) =4 G . 15.25
1"2(:ir(r dr N p l )

Making use of eq. 15.23. we see that eq. 15.25 becomes

d2 = m. (15.26)
dr r2

In spherical coordinates. V¢ = g? and eq. [5.24 can be written as

til-‘0'} _ _ (Li—11>
dr — pdr

= _fl’§fl, (15.27)
r

after making use of eq. 15.26. Equation 15.27 is lcnown as the equation ofhydrostatic
equilibrium.
Rewriting eq. 15.27 as
2
UL“ = 4mm (15.28)
p dr

2. For the vector in different coordinate systems. see Appendix I.

430 Gas Dynamics. Gravitational Collapse. and Stellar Winds

and differentiaiing eq. 15.28 w.r.t. r. we have

ld rzdP(r))_
,2d,(p d, — 4"GP(')- (15.29)
after making use of eq. 15.23. If we assume an equation of state of the form in
eq. 15.14, eq. 15.29 becomes

£1
.25, [flash
p 5.] _—__4Ham , on»
Equation 15.30 is an ordinary differential equation and can be solved once the
boundary conditions are specified. As a first step. we can express eq. 15.30 in a
dimensionless form by introducing two dimensionless variables.
r
t-; (15.31)

and

_ Ttr)
a _. Tc . (15.52)

where a is a characteristic unit length, T0) is the temperature at radius r. and Tc is

the temperature at r = 0. The density. expressed as a fraction of the central density.
can be obtained from eq. 15.14:

P _ P ”1’
_(Pc) . (15.33)

Making use of the ideal gas law (eq. [5.9). we can write eq. 15.33 as

(P/PJl—Uy = mm". (5.54)

With eq. 15.32. we have

:2 = new"). (15.35)
r—1

9 = (fl) . (15.36)
P:

Defining

1
n ; (15.37)
 15.2 SeU—Gravt'tating Hydrostatic Spheres 431

and substituting eqs. 15.3] and [5.35 into eq. [5.30. we have
1;"1
EiflfliL $1.2fl)__n
[ 4rrGa2 ]:2d¢ (6 dc _ 9' (1533)

Eq. 15.33 is now a differential equation expressed in dimensionless variables. This

implies that the value inside the square brackets has to be dimensionless. Since the
scale length a is yet to be specified. we can simplify the appearance of eq. 15.38 by
defining a in such a way that the value inside the square brackets is unity:
1;: 1/2
a: [em] 47rG
0539,
The resultant equation

.11 (if 2E
(zdf __ 0 n
d§)_ (15.40)

is known as the LanevEmden equation. The only parameter in this equation is n. which
is known as the paiytropic index. Analytic solutions to the Lane—Emden equation exist
for n = O. l, and 5. For example. in the case ofn = 0.

_. =fi C .
d6 (C d6) 1 .4 1)
(5

Upon integration. we have

2‘19 f3
3 + C.
—=———
6 d: ( 15.42 )

Al the center of the sphere, T = Tt, p = pc. or 6‘ = 1. Since there is no gravitational

attraction at r = 0. the pressure gradient must also be zero according to eq. 15.27.
From the equation of state (eq. 15.14). the density gradient must also be zero:

dP
(d—r)¢=o' (15.43)

or dflldfi = 0 at i: = O. The integration constant C in eq. [5.42 is therefore zero.

Eq. 15.42 can be integrated to give
(2
—30=—2—+C. (15.44)

Due to the boundary condition 9 = lat f = 0. C = -3 and eq. 15.44 becomes

:1
6(£)=1-—?. (15.45)
432 Gas Dynamics, Gravitational Collapse. and Stellar Winds

if we define the outer edge of the cloud (R) as the radius at which the density and
temperature go to zero. the outer radius is therefore 6 = 4/5. Equation 15.45 lhflcfou;
describes the temperature profile of the cloud from the center (6 = 0) to the outer edge
(f = {I = J6). From eq. 15.35. the density profile can be determined accordingly,
The total mass of the cloud is given by the integral of eq. 15.23:

5(0):]; 47rp(r)r2dr. (15.4.6)

Substituting eqs. l5.31 and 15.35 into eq. 15.46 leads to

at
mat) =£ 4H(a€')2(pc9”)d(a§’). (15.47)

C
M(.5)=4:ra3pffo fi’29"d§'. 05.48)

Comparing with the Lane-Emden equation (eq. 15.40). we can see that the integrand
in eq. 15.48 is an exact differential and the mass function is therefore

(M t
3 c(_ E '2_)
M (if )_4 nap {I a

= 4193p: (—62%) . (15.49)

Since Ihe density is maximum at the center and decreases outward. the density gradient
(dB/d6) is always negative. which implies that the mass function is positive. In the
n = 0 case, -¢2d9/dc = 53/3 (eq. 15.42}, giving

mg) = 4na3pc (cl/3) . (15.50)

Since R = at]. the total mass of the cloud is therefore

41" 3
M(R)=?p,R. (15.51)

So forn = 0, the central density is the same as the average density (density is constant).
as is expected from eq. 15.35.
For n = I. the Lane—Emden equation can be written as

do:
_ we
__ 9 =0_ (15.52)
dc: + E d: +
 I52 Self-Gravitating Hydrostatic Spheres 433

which is a special case of the spherical Bessel equation,

fly 2 dy [ ]._—
_.+__+ e(£+1)] =0.
15.53
d):2 x dx 12 y ( )
A particular solution for E = 0 is

.1000 = 5mm. (15.54}

I

which satisfies the boundary conditions y(0) = l and y’(0) = 0. Therefore we have
the solution for n = l.

3 = Sin“). (15.55)
6
Since the first root of eq. 15.55 is Jr. the outer boundary of the cloud is {I = 1r. Differ-
entiating eq. [5.55 w.r.t. :5. we obtain the value of —¢2d0/dt§ = If at 51- Substituting
this result into eq. [5.49, we have

:22 M(R)
P: = (T) a}. (15.56)

or the central density is 3.29 times the average density ,5.

The only other analytical solution to the Lane—Emden equation is for n = 5.
which is

9= (15.57)
3+?
For other values of the polytropic index. the Lane- Emden equation has to be solved
numerically. We can see from eq. l5.57 that it does not have an outer boundary
(5 —> on at 9 r 0). In fact all solutions for n 2 5 are unbound. The solutions of
the Lane—Emden equation for n = 0. LS, 2.0. 2.5. 3.0. 3.5. and 4.0 are shown in
Figure 15.1.
A series expansion approximation solution is given by

12 u ,4 n2 n ) 5
3:1——65 — ——
+120“; +( 1390+3024 5
61:13 61112 n s
+ (1.632.960 — 1.083.640 + 46,656): + - -- ( 15.53 )
The constant term is l as it should be. for at C = 0. 9 = l, or p = p5. For n = 0.
eq. 5.58 reduces to eq. 15.45.
Of particular interest are the cases of n = 3/2. corresponding to y = 5/3 for a
monoatomic gas. and the case of n = 5/2, corresponding to y = 7/5 for a diatomic
434 Gas Dynamics, Gravitational Collapse. and Stellar Winds

1.0 1—rltII—I—I'IIrrirr—r—rli—tiiliiil-l—Illlri‘llillrlulll—I—r-

0.9 — _

0.3 — j
I. -_ J
0.7 - 3-» ..
_.
'-l‘.‘
0.6 — "N“,- _
'.l\‘ \‘k
- ',-\{\t‘ -.
9 0.5 — '. {:s‘ -
_ 'l \ \\u‘\
. " \ n.

04' - '.
\“\.“~
\\‘_\ \‘X‘ -'
- '_ \ \ \‘\\ x '
0.3 — .- .‘
\\ x\ ‘ \ \‘\ \‘\‘
_J

02 _ n
=0 I: \\ \ ‘ ‘X
\- ‘3‘““- ‘~._‘ —
_ ' =\ \ \_\ H. M “-5“- ”=43

.\ \ . ‘-... ‘‘‘‘‘ 11—.

0.] ._ a.» \ .9 - a a.“ ‘--—.:35 _
‘ 'U‘ \ \\ ‘ :‘t fi'n ........
.‘ \eo ‘ 5'; “435519 "-
00 Ill—Llllllll llItltllLLttTXJIIJIr‘r-utliililiTT'r-l-qgll

0 I 2 3 4 5 6 7 8 9 IO

Figure 15.1
Solutions to the Lane-Emden equation for n = 0. LS. 2.0. 2.5. 3.0. 3.5. and 4.0.

gas. Forn = 3/2. c. = 3.65375 and [-€2(d6/d£f)]a = 2.71406. Fora gas cloudoflOO
Meand radius 1 pc. eq. l5.49 gives a central density of ~ 10‘” g cm". or ~ 5300
crn‘3 if it is made up of pure hydrogen (p. = 1). For n = 5/2. the componding values
are pf = 4 x 10'20 g cm 3. or ~ 23.000 atoms cm'3.
The polytropic approach to determine the hydrostatic structure of spherical gas
clouds has been applied to stars, stellar clusters, interstellar clouds, galaxies, and
galaxy clusters. Although a galactic cluster can be described as a collection of colli-
sionless gas. and the particles {individual galaxies) do not create pressure as such (and
therefore have no equation of state). they do have a velocity dispersion. This velocity
dispersion makes the cluster behave like an isothermal hydrostatic system.
An example of an isothermal hydrostatic system is the dark cloud 363 (Fig. 10.4}.
From eq. I534, we can see that

(T/ Tc) = (in/pay". (15.59)

Therefore, for an isothennal. self-gravitating system. y must be equal to 1. com-

sponding to a polytropic index of co.
 15.3 The Win! Theorem 435

15.3 The Virial Theorem

Although the Galaxy is a dynamic place active with inflows and Outflows. many of
the subsystems of the Galaxy can be considered to be in an approximate state of
dynamical equilibrium. In our everyday life. we hold gas or liquid in place by placing
it in a bag or a box. But in the lSM, there is no such means of confinement. and
gaseous bodies stay in a fixed volume of space by a delicate balance between gravity
and pressure. An example of such equilibrium configuration for a polytropic gas was
discussed in the last section. In general. a gravitationally bound system needs to
possess a kinetic energy due to either thermal motion (through collisions). turbulence,
or velocity dispersion (for a collisionless gas).
The behavior of a system under dynamical equilibrium can be described by its
global properties such as total kinetic and potential energies. Beginning with the
equation of hydrostatic equilibrium (eq. [5.27) and multiplying it by 41rr3dr and
making use of eq. l5.23. we have
G Md M (r)
4m3dp = . (15.60)
r

Integrating over the entire cloud, we have

P, M
3f vap = —f M, (15.61)
PI." 0 r

where P, and Pc refer to the surface and center of thecloud. and M is the total mass of
the cloud. Using the technique of integration by parts and recognizing that the volume
at the center is zero yields
v M
4nR3P, —3f
0
PdV=—fo M. f
(15.62)
Assuming that the cloud is in the ISM where the density is so low that the P, can be
considered to be zero. we obtain

3] EdM+9=tl (15.63)
where we have made use of mu = pdV and S2 is defined by

9 = _ f“ GM(r)dM_ (15.64)
0 r

We can recognize that the first term of eq. 15.63 represents thermal energy and the
second term S2 is the gravitational potential energy from eq. 15.64.
Substituting eq. IS. 16 into eq. 15.63, we haVe

3(y — 1) f UdM + 9 =0. (15.65)

436 Gas Dynamics. Gravitational Collapse. and Stellar Winds

Since 1.1 is the internal (thermal) energy per mass.

30» — DU +9=0- (15.66)

For a monoatomic gas (y = 5/3). eq. 15.66 becomes

2U + .Q = 0. 05.67)

The result above is commonly referred to as the vin'al theorem.

The total energy (E), defined as the sum of the kinetic and potential energies. can
be expressed in terms of either the thermal energy or the gravitational energy through
the virial theorem:
E=U+Q
= —U
= 9/2. (15.6%)
Since the gravitational potential energy is always negative, the total energy is also
negative. The v'trial theorem requires that as IQI increases, U also increases. Therefore
if a cloud contracts, S2 becomes mere negative, and the cloud heats up.
For particles other than a monoatomic gas, the total energy can be expressed in
terms of tlterrnal energy through the generalized vitial theOrem (eq. 15.66).

E=—3(y—l)U+U
= (—3}: + 4w. “5-691
or in terms of potential energy.

E = Q - Q
3(1’ - I)
= V "4/39. (15.70)
y — 1

So a self-gravitating gas cloud is bonnd (E < 0) only if y > 4/3. A cloud made up of
gas with y < 4/3 cannot remain a stable entity under self—gravitation.
We note that in a polyatomic molecule consisting of five atoms. there are 3
degrees of freedom due to translational motion, 3 due to rotations. and 2N — 6 = 9
degrees of freedom due to vibrations (Chapter 8). For a gas made up entirely of such
molecules. then y = l+ 2/l5 = 1.133. Since y is less than 4/3. such a molecular
cloud will not be stable.
A cloud under dynamic equilibrium needs to constantly adjust itself in order to
maintain stability. From eq. 15.66, we have an expression on how the kinetic energy
will change with changing potential energy:

dfl
dU= _ , (15.71)
3(1/ - l)
 I5.4 Pressurel’ess Gravitational Collapse 437

Since the total energy is directly proportional to the potential energy (eq. 15.70). cloud
contraction will lead to a decrease in total energy:

dE= -11” IQI. (15.72)

y—l

In order to satisfy the virial theorem and obey the conservation of energy, the excess
energy has to be radiated away. Out of the change in 9. the fraction 1/3(y -— 1) of (K!
goes into internal energy, and the fraction (y — 4/3)](y — I) is radiated away. We
note dial the larger the value of y, the higher the fraction of potential energy change
is radiated.
For a uniform-density cloud. the gravitational potential energy can be calculated
from eq. [5.64.

9 ft G(%Epr3)(4nr2pdr)
0 l"

2
= 2—0“ _ (15.73)
5 R

If a molecular cloud of total mass 100 M3. and radius 1 pc contracts to half of its
size, the change in potential energy is 5 x 1044 erg. If y = 5/3. half of this amount is
radiated away. If y = 7/3. 3/4 of this amount is radiated away.

15.4 Pressureless Gravitational Collapse

In the hydrostatic case above. We assume that the attractive gravitational force is
balanced by a repulsive pressure. defined by the equation of state. In the absence of
such pressure. the gas cloud will undergo gravitational collapse. or a free fall. The
acceleration of a particle at radius r is determined by the total mass within this radius:

'r': -6542"). (15.74)

r

For a particle initially at rest on a surface of a sphere of radius r0 with a total mass
M, the total mass within radius r(r) is always a constant as the sphere undergoes
gravitational collapse. Equation 15.74 can be integrated by multiplying both sides by
r and separation of variables:

'1’
d!
=a: [26M
1'
— 26M.
To
(15.75)
433 Gas Dynamics. Gravitational Collapse. and Stellar Winds

where we have made use of the initial condition 1" = 0. r = r0 at t = 0. If the initial
density distribution in the sphere is constant, the initial density p0 is given by
M
.00 = m- (15.76)
T'o
Choosing the negative root in eq. 15.75 to correspond to a collapse solution, we have

dr BirG r
—- = -ro p° (—° — I). (15.77)
Introducing a new variable a where r = r0 cos2 u. i = -—2ro(cos u sin thi. eq. 15.77
can be written as

du 1 8n Gpo
- (15.73)
5—2coszu 3

Defining the free-fall time (:5) as tlte time needed for the particle to fall to r = 0,
eq. 15.78 can be integrated to give

u sin2u %_tfi 8116,00

[2+ 4 :io—Z" 3 . (15.79)

where we have made use of the boundary conditions it = 0 at r = 0 and u = 1:12 at

r = tfi. The free-fall time is therefore

l 31:

For a gas cloud with an initial density of 1000 H: atoms enrl. the free-fall time is
~ I million years. We note that the free-fall time is independent of the initial position
1-0. and is a function of initial density p0 only. So no matter where a particle is, it takes
the same amount of time to fall to the center.

15.5 Gravitational Instability

In a real interstellar cloud. the pressure is never zero because there is always positive
gas pressure if the gas temperature is finite. The stability of a cloud is the result of
a balance between the gravitational force and the thermal pressure (Section 15.3).
When gravity exceeds thennal pressure. gravitational collapse will result. From the
condition 2U + Q < 0 and malo'ng use ofeqs. 15.9, 15.10, and 15.73, we can see the
collapse will occur if

3MkT 30m (15.31)

<
umH SR
 15.5 Gravitational Instability 439

For a uniform-density sphere, we can express R in terms of M by using eq. 15.76.

After eliminating R in eq. 15.81. we have

3/2 in
M>( Gum“
5” ) (A)
41mg
(15.32)
This condition is referred to as the Jeans criterion. and the right-hand side of eq. 15.82
is called the Jeans truss.

3:7. 1,1'2
M,=( Grim“
5” ) (L)
41rpo
(15.33)
From eqs. 15.66 and 15.16 we can see that the Jeans criterion is independent of y, and
the Jeans mass has the same expression for atomic or molecular gas. For a molecular
(u = 2) cloud with initial density of 103 cm 3 and temperature of 20 1c the MJ has
a value of 65 M0.
The Jeans criterion can also be expressed in radius instead of mass. Making use
of eq. 15.76 and eliminating M in eq. 15.81, we have
112
R , (i) _ (15.34)
4JrGumeo

where the right-hand side of eq. 15.34 is called the Jeans length. For the same
parameters as aboveI the Jeans length is 0.68 pc.
Using the definition of sound speed (eq. 15.21). we can express the Jeans length
as

1502 in
RJ = D (15.85)
413me

Since the sound travel time across Ihe cloud

& ,_ 15
(15.86)
no 4erGpo

has the same form as the free-fall time (eel. 15.30). the Jeans criterion is therefore
equivalent to the sound crossing time being of the same order as the free-fall time
under pressureless conditions.
In Section 15.1 we saw that a fluid of uniform density initially at rest and under
pressure equilibrium will develop a sound wave as a result of a slight disturbance.
In the presence of a force (such as gravity). the fluid may deviate from pressure
equilibrium and generate an instability. By adding a gravity term (eq. 15.24) to
the equation of motion (eq. 15.2). J. H. Jeans was able to show that the sinusoidal
perturbation will grow exponentially if the wavelength of the perturbation wave is
greater than the Jeans length. Such an instability initiates Ihe gravitational collapse
of the cloud.
4-40 Gar Dynamics. Gravitational Coilapse. and Stellar Mud:

15.6 Stellar Winds from Hot Stars

The opposite of collapse is expansion. and an example of systematic expansion motion

is stellar winds. 1n the simplest case where the thermal energy exceeds that of the
gravitational potential energy. gas will "evaporate" from the surface of stars. From
in situ Observations from spacecraft, we know that the Sun has a solar wind. The solar
wind has a velocity of several hundred km s' 1 and a mass loss rate of ~ 10—[4
yr". While the solar wind has a strong effect on the Earth‘s environment and the
interplanetary medium, it does not have a strong impact on the ISM. Stars of high
temperature. in particular. 0 and B supergiants. Wolf Rayet stars. and central stars
of planetary nebulae, have much stronger stellar winds. Massive stars. even when
they are still on the main sequence. have mass loss rates that are comparable to their
nuclear burning rates. Over their lifetime, most of the original stellar mass is ejected
into the ISM in the form of a stellar wind. and because of the momentum and energy
they carry. these winds have significant dynamical effects on the ISM.
Stellar winds from hot stars were first discovered from rocket observations
through the detection of P Cygni profiles in UV resonance lines. P Cygni profiles
consist ofa blue-shifted absorption component and a ted-shifted emission component.
A stellar wind creates a circumstellar envelope around the star. Along a line of sight
toward the star itself. we see a column of gas maving toward us. This colurrur of
gas absorbs the stellar continuum and creates an absorption line covering the range
of Doppler-shifted wavelengths from the stellar velocity (11.) to v, .. um, where van
is the terminal velocity of the stellar wind. The entire circurnStellar envelope also
scatters the stellar photons. creating an emission profile with velocities ranging from
u... — van to v, + noo (Figs. 15.2 and l5.3).
In a spherical. steady stellar wind, the density distribution and velocity field are
not changing with time. and the first temts on the left-hand side of eqs. 15.4 and 15.5
can be set to zero. Assuming that the only forces present are the gas pressure and
gravitational force from the central star. eq. 15.5 can be written as
do 1 dP GM.
.— + .__. + = 0. I537
ud'r ,0 dr r2 ( )
where M, is the mass of the central star. From the equation of continuity (eq. 15.4).

ld_P=__ld_”_3 (15.88)
pdr udr r.
Making use of the ideal gas law and assuming that the flow is isothermal, we can write
eq. 15.87 as

74,1 GM
1 g _ (T - 7*) (15.39)
v dr _ v2 - a2
where a is the isothermal sound speed (eq. 15.22. y = 1). We note that the denominator
on the right-hand side of eq. 15.89 is zero when u = a. The radius at which this 0'69"”
 I545 Slellar “findsfmm Ha! Siam 441

NGC 6543 SWPI897 4 min

4.0 - 10“ - - . —~ . ~ .

3.0- 10“ -.
g 5
I: :
3 1
E 2.0- 10-" 1
.43 :
a
U i
1.0 - 10-“ i

o 1 n a a q

I200 i400 1600 1000 2000

Wavelength (A)

Figure 15.2
The IUE spectrum of the central slar of NGC 6543. showing the pmsencc of a stellar wind.
Four lines can be seen showing the P Cygni profile. The venica] scale is in units of erg cm 2 s"
A“ [from Feibclrnan 1994. PASP. 106, 756).

2.05.“ ....,...—.—,....—r....—r_.

[55-11

BLUE-ll . I
E " ‘ ‘ i a
E Clvabs
fiSDE—IZ '
U - ‘15.
Cl
‘15.

4' - 1n - _l.- I.. ._

-5.0E—I2 ‘
1535 1540 1545 1550 1555 [560
WavelengtMA)

FigurelSJ
[fish-resolution J'UE spectrum of 1C 418 showing the P Cygni profile of C Iv (from Hyung e:
at. 1994. PASP. 106, 745).
442 Gas Dynamics. Gravitational Collapse. and Stellar Wmds

is referred to as the sonic point. The Only way to avoid a divergence is to have the
numerator also go to zero. implying

r =rc= .217_ (15.90)

Therefore a solution to eq. 15.89 exists only if u(rc) = a. Under this solution. both
the numerator and denominator on the right-hand side of eq. 15.89 are negative rm
r < re, and both are positive for r > 'c- Consquently. the velocity gradient always has
a positive slope and the solution is subsonic (v < a) for r < rt and supersonic (u > a)
for r > rt. There is only one transonic solution to eq. [5.89.

15.6.1 Radiation Pressure on Resonance Lines

as a Mechanism of Driving Hot Star Winds
Since massive stars are luminous. it is plausible that the stellar winds are driven by the
stellar radiation field. Since the radiative force decreases with distance as r‘z, it can
be considered as a negative gravity. By introducing a dimensionless inverse-square
repulsive term F for the radiation pressure term. we can write eq. 15.89 as

la' 1:
__—-—._-_
1 [2a 2 GM.“ ._ l‘)]_ (119])
r r1

The most obvious source of opacity is electron scattering (Section 5.7). In this case
the wind is driven by the stellar continuum and I" would be a constant. This was
considered by Eddington in his study of luminous stars. where the effects of radiation
pressure can be signifith as a counterpressure of gravity. However, most atoms
are ionized in the atmospheres of hot stars and there exist many strong lines when:
the stellar radiation can be absorbed. The opacity of these lines can be many orders
of magnitude larger than the electron scattering opacity. allowing for the transfer
of photon momentum to the gas. Although these strong lines can be saturated and
deplete the stellar continuum radiation at their rest wavelengths, once the gas is
accelerated, the Doppler often allows the atoms to absorb fresh radiation from slightly
shorter wavelengths. This makes possible a continuous acceleration of the gas until
the terminal velocity is reached.
The optical depth for a photon of frequency v0 along the line of sight to the depth
r0 in the stellar wind is given by
on

19000) = f n ,-(r)avdr. (15.92)

ro

where nj is the number density of atom A in the lower level j and

_ n22 _ _ 3}":0)
av — mec—fjt [1 gin}(r):| 4’1:
 15.6 Stellar Mndsfmm Hot Stars 443

(eq. 5.45). For an accelerating stellar wind. the optical depth at each frequency is
appreciable only over a narrow range in radius where that frequency is matched by
the Doppler—shifted rest frequency (no) of the line. in the extreme case 4:5,, is a delta
function: this is known as the Sabolev approximtt‘an.
Let us assume that the line has an intrinsic width of 2Au; then the normalized line
profile has the form ¢u = l/(2Av) over this width but zero outside. In a stellar wind
with a velocity gradientdu/dr, the optical depth corresponding to frequency v0 would
be nonzero around radius r0 over a depth of Ar = AU(dl’/dv) where Au = 2cA v/va.
In this approximation. eq. 15.92 becomes
2 . _
run(ro) 2 %ffl [1— g’n'(r°}] evn1(ro)Ar
Sifljb‘o)

_ n22 3}":‘(Tol 1 km; (dr

' :ij" [1 _ snare] (E) "1"") ( v0 ) d»)...
__ _ sjn- (’0) _ f. (cl—r)
miffl- [I 3.11th’tfl] n,(r0)v0 (1:: m. (15.93)

Since the momentum of the photon is given by E/c, the radiative force. given by
the rate of change of the photon momentum flux. is therefore the product of the radial
component of the intensity and the absorption cross section divided by c integrated
Over all angles. At large distances, the star can be assumed to be a point and all
radiation. and therefore the radiative force, is radial. 1n the optically thin case. the
stellar flux at radius r is
R 2
F.b(r) =1rB..U(T.) (7') . (15.94)

Since the radiative force is proportional to the total number of atoms (N1) available
to absorb,

a T. 2
Ffld(vo)=:-# (Rf) Njav. (15.95)
The radiative acceleration on a stellar wind with density p at distance r is given by
the radiative force Over mass.
In(T) 2 n-_Ja
Hm(l’o)= — (—) . (I596)
c r p

Smitvo) (in units of cm 5‘2 Hz‘ ') represents the radiative acceleration per frequency
due to line absorption and when integrated over frequency can be added to the
left-hand side of eq. 15.37 to find the solution for the velocity profile. Since every
atom receives unattenuated radiation from the star. the radiative force is therefore
proportional to the particle density and is independent of the velocity gradient.
444 Gas Dynamics. Gravitational Collapse, and Stellar Winds

In the optically thick case every photon in the frequency interval Av is absorbed
over distance Ar at distance r. The total flux absorbed is given by
T 2
F: ————,r3u0(
J (fl) AD
C r

__ tritium) R_ 2 Ar du
- *c— (T) “07.7,- “5-97)
The radiative force is the flux absorbed times the total area AA divided by c, The
radiative acceleration is given by the radi alive force divided by the total mass available
to absorb in this volume. Since the total mass is pAAAr, the radiative acceleration
at distance r is therefore

man (a)? 3914»

8m = (15.98)
c r c ,0 dr '
We note that the radiative force is entirely dependent on the velocity gradient in the
wind and not on the particle density. Since in general. many lines at different v0 are
available to absorb the stellar continuum radiation. the total radiative acceleration is
the sum of the contributions from different lines. If the density of spectral lines is high
enough. it is possible that much of the stellar continuum is used to drive the expansion
of the stellar wind.

15.6.2 Derivation of Mass Loss Rates from Line Profiles

The mass loss rates of massive stars can be derived by comparing the observed P Cygni
profiles with theoretical profiles constructed assuming a velocity law and ionization
structure. However. the derived rates are uncertain due to problems associated with the
excitation and ionization states of the atoms observed. This is further complicated by
the fact that some stars. for example. Wolf ‘Rayet stars and central stars of planetary
nebulae. have nonsolar composition in the atmosphere because of previous stages of
nuclear shell burning. Mass loss rates obtained from the fitting of the line profiles
range from 10'5 MgJ yr 1 in GB supcrgiants to 10“ MG yr‘I in Wolf—Rayet stars.
Modern analysis of stellar winds from hot stars incorporates a complete modeling
of a spherically symmetric. radiation driven. expanding atmosphere. The model
solves the hydrodynamic equations, radiative transfer. and the rate equations of the
atomic species under non-LTE conditions, all in a self-consistent manner (Fig. 15.4).
Depending on the velocity law. spectral lines of different ions will shift to different
wavelengths at different heights of the atmosphere, therefore interfering with each
other. These effects of line blocking and line blanketing need to be carefully heated
in the solution of the radiation transfer equation.
Due to the high quality of UV spectroscopic data available. these models can
be constrained to yield accurate stellar wind parameters. Figure [5.5 shows the
Copernicus and WE Spectra of the 0 supergiant HID 306M (at Cam). By fitting the P
Cygni profiles of the resonanace lines of C, N. 0. Si. S. P. and other metal ions. onecan
obtain stellar parameters (Terr = 29,000 K. log 3 = 3.0, R = SORO. M. = 33 MG) 33
well as wind parameters (M = 4 x 10"6 M0 yr‘l, um = 1500 km s“). These models
 R. Z

r L
flydmdymmlcs
M r: 41tr1 pv
6." -92 L _
dr _ dr P + g“ 3
n. - el
3,“ =3,” + —--°°;“ 25.3, (g - 8—) f / I,(fl)flV}pdpdv
liner ‘ “ o -I

can" Rate equations

"r ’
”1""?
Radiative
'_ V trawler
axon“ + q.) + afar... + C“) (5“ -13.; =
jlr'
' ______ n r3! 1 —fl, (9’
I —- __v = _z
UHF-:1 ' a, r or
= 2 mar“. + C”) + n.(R..- + cm.) I
pr

5
__________________ 53
I V

: Shock physics |__| —x'

I I V
.——.1 p1 '

E SE #4“; fun) i an. “on

r—————————————————i-'«'
: K-shell ionization ; |
E d 1 1'” fl5|“.

u; + ”a; (F) =
L...I E ‘, 1
x: = lat: %__ _ "
p/D 4“! (JV
_ Sr) (IV
E er'n F :

I_________________ J

M v(rJ

Synthetic spectrum

Figure [5.4
A schematic diagram illustrating the integration of systems of equations to fit the line profiles of
Stellar winds from hot stars. From the input stellar parameters (temperature. radius. surface gravity.
and rrretalliciry). one can produce a spectral energy distribution and synthetic spectrum to compare
with observed line strengths and profiles in order to derive the mass loss rate and wind velocity profile
(from Pauldrach 2GB. Rev. Mod. Ann. 16. HI).
 .22 .mfi .53. .88 .3 a 35.3 55 33...
Egg 5.2u ~55? Pies . .3 33 me. E... 33535 .3 song“... a: He“ .50 a be £309.." >= 2:.
92 0.5M.“—
Evans—”:3
oom— onE 82 On: 8....— 002 82 Onfl 8w—
. _ _ -| _l_| — _ O
, ._ ; . ...... _ . ,. no
r
. _ .
p . ._ . . .
.
. .. a
... _. i 1
.....-
.
r
. .
._ . ...... . . .. _
...
.
_ o..—
1 n...
....z :0: EU
_ LI : .D.N
Ga: Dynamics, Gravitational Collapse. and Stellar “find:

OS— 82 82 One. 83 an? 8m. on? com—

J _ . .. 4| In _ a .. O
_ . . .n. . .
. ....... . _ .. ,
_.L a . no
_.__ ... _.__. _.__. L .2. . _ . . . ... . ._ , .
.H
___ . . .... . ...W . . .... . .. . _._ .. 1‘. . ._ ...“... 5.? _ T... _ . . j _ o; W
.- . . . _ i, _ L 4 m
- ._. . 43
EU >m _>__m >0 to ___0 >2 him
2 . _. _L _ _ _ . QN
8m. 03- con. on: OJ: 0mm: 80— 9.3 can
A . . .. _ _ _ WI ‘ . . q o
_ _ . . . ___ _;.“x... . ; ’_._ - nd
“r. ...: _._ .... . . ... ... .. k; . .. _. .. ._ . m : _ . _. .
‘ . . A. _ :. y . . . .. ... . _ _fl _ .... . o.—
.. H U 1 n;
50.2 __ZwEZEU .... 2m 50 ___Z=_U>_Z>__.__>m>_z
\— = I . . - _I L _ I: - _ . _ - I 0.”
II Hanging m .32: + 8.6 3 38m a:
446 we
 [5.6 Stellar Windrfmm Hat Stars 447

confirm that radiation pressure on resonance lines is the driving mechanism of winds
from hot stars. In addition to obtaining wind parameters. these models can also derive
the abundances of ions. as well as basic stellar parameters such as mass and distance.
Stellar winds from massive stars represent a significant input of mechanical
energy into the ISM. The effects of these winds on the ISM will be discussed in
Section 16.4.

15.6.3 Derivation of Mass Loss Rates from Free-Free Radiation

Stellar winds ejected by hot stars are often photoionized by the Lyman continuum
photons from the central star and therefore emit f—f radiation. Since the electron
temperature of the ionized gas is not highly dependent on the distance from the star
(Section 6.5), the source function can be assumed to be constant. and the emergent
flux at distance D is given by eqs. 2.79 and 2.80:

R
F”: [a .315?“ —-e '(P))27rpdp. (15.99)

where R is the maximum extent (outer radius) of the stellar wind and p is the impact
parameter of the line of sight from the central star. If we write eq. 6.25 as xv = Kurt}
then

M
I'(p)='K1: —\/1‘?2Tpi n30) dz, (15.100)

where K” = 0.0177301. Tent—27:3]21; 1 cm5 and z is the length element along the
line of sight. In a stellar wind, the density distribution is given by the equation of
continuity

M
= 4Hflempr2U(T)
———,
11:0) ( 15.10] )

where M is the mass loss rate (in units of g s"). For constant M and u.

_ _M'._
n, 4np‘mHur2

= 52, (15.102)
:-

where A = M/4xptemflv. By making use of the relation

z=‘/r1—pz, (15.103)
443 Gas Dynamics, Gravitational Collapse. and Stellar “find:

we can write eq. 15.100 as an integral over 1':

TU?) 1f __ . R dr
—tt (ram) (15.104)

Making a change of variable 1- = p seed and assuming R —> on. we can integrate
eq. 15.104 to give

tr 1(qu
I‘ (P) = —
2 p3 . (15.105)

Substituting eq. 15.105 into eq. 15.99, we have

11’ 21'3 A 4/3 on _ 1

Fv=21r (E) Faummffl xfo (1 —e 3) ydy. (15.106)

The integral on the right has a numerical value of 1.33. Since K" o: u‘z. B” o: v2 in
the Rayleigh—leans limit (tin/k1; << 1). F, e: um. The free-free spectrum from an
ionized SlCIIaI' wind therefore has a Spectral index of 0.67 in the radio regime. For
T, = 104 K.
. _ 4/3 2’}

.
F.=23
(Mt/Mm)"5‘5]
[ll-Jul
—-————'
') (11/ H z)
213(3u)
—
x, ( D I k pc)
—1.l . 1 .
y (5107)

The radio spectrum is flatter than that of a finite-size nebula because one sees into
different depths of a stellar wind at different frequencies. Because the absorption
coefficient is higher at low frequencies. the size of the optically thick surface is larger
at low frequencies. This translates to a larger flux at low frequencies than in the finite-
si2e nebula case.

15.? Winds from AGB Stars

The first evidence of large-scale mass loss from AGB stars emerged as a result ofthe
development ofmid-infrared detectors. A number of stars were found by photometric
observations to be much brighter in the infrared than in the visible. and to have very
low (~ 600 K) color temperatures that could not be due to photospheric emission.
The most likely interpretation is that these stars are surrounded by thick dust shells
that absorb the visible light from the stars and reemit it in the infrared (Section 10.3).
Narrow-band photometric observatioas in the N-band window show that there is a
well-defined emission feature at the wavelength of 10 am in a number of cool stars.
This feature is commonly found among red giants with spectral type later than M3 and
is identified as emission from silicate grains (Section 11.2.1). Chemical equilibrium
calculations show that silicate grains should be the first solid particles to condense in
O-rich stars (Section 13.1). For carbon stars, the first condensates should be carbon
and silicon carbide (SiC). The 11.3-ttm SiC feature was subsequently detected in
carbon stars (Section 11.2.4).
 I5. 7 Windsfrom AGE Stars 449

Although early observations of infrared excesses were limited to known optical

M stars, the Air Force Geophysical Laboratory (AFGL) rocket survey of the sky
at If) and 20 um discovered that many sources with large infrared excesses had no
opu'cal counterparts. Ground-based follow-up observations showed that many of these
sources are late-type Stars with thick circumstellar envelopes that completely obscure
the central star. Because of the high opacity of the grains. they experience significant
radiation pressure and cannot remain stationary with respect to the star. Thus. there
is no doubt that the infrared excess is a clear manifestation of mass loss.
Spectrophotometric observations of Mira variables and infrared stars discovered
in the Two-Micron Sky Survey (IRC) and the AFGL surveys show that the silicate
feature goes from emission to deep absorption. which is the result of an increasing
optical thickness in the silicate band (Fig. 10.7). The fact that objects with silicate
absorption features often have very red colors supports the hypothesis that these
objects are undergoing mass loss at a high rate.
Mass loss on the A63 is also manifested in molecular emission. Many oxygen-
rich AGB stars are found to have OH maser emission (Section 7.10.1). The DH
emission often shows a two-peaked profile. which is a result of a steady mass loss
process with the expansion velocity of the envelope being given by half of the velocity
separation of the two peaks. Some 0H sources associated with infrared sources
discovered in the [RC and AFGL surveys have no optical counterparts and are known
as OHJIR stars. Since the publication of the IRAS Point Source Catalog. searches of
IRAS sources with colors similar to known OH/IR stars have yielded many more 0H
sources. There are over 2000 OHIIR stars in the Galaxy.
The correlation of variations between the OH and infrared fluxes suggests that OH
masers are pumped by infrared photons (Section 7.10. I ). Monitoring of the variability
of a group of ~ 50 unidentified OH/IR stars shows a mean period of l000days. much
greater than the mean period of 350 days for optical Mira variables. Since only ~ 30%
of optical Mira variables have 0H emission, it is likely that OH emission develops
only when the mass loss rate is high enough to create a saturated maser. and OHIIR
stars probably represent stars further up the AGB than optical Mira variables.
Thermal CO emission from AGB stars was first detected in 197 l. The observed
”CO and ”CO profiles in the carbon star CW Leo (IRC+102 16) show characteristic
flat-topped and double-peaked profiles. which were respectively interpreted as the
optically thick and thin cases of the thennally excited molecular spectra in a partially
resolved circumstellar envelope created by continuous mass loss (Seetion 15.7.2).
Subsequent CO surveys have resulted in the detection of several hundred AGB stars in
the J r l - 0, 2 — l, and 3 - 2 transitions. Mass loss from AGB stars is now believed
to be the dominant source of mass input into the ISM. From the obserVed mass loss
rates and the total population of AGB stars in the Galaxy. the total rate of return of
mass by AGB stars in the Galaxy is estimated to be ~ 0.3 M 3 yr' l.

15.7.1 Radiation Prefiure on Grains

as a Mechanism of Driving AGB Winds
Mass loss mechanisms for AGB stars can be generally classified into (i) thermally
driven. (ii) wave-driven. and (iii) radiation pressure—driven. Since stars with high
maSs loss rates all show large infrared excesses (Sectioa 15.7), it is likely that grains
450 Gas Dynamics, Gravitational Collapse, and Stellar Winds

play a role in the mass loss mechanism. For a dust grain with radius a and radiation
pressure efficiency Q!Jr (eq. [0.14). the radiative force on it from a star of luminosity
L, can be found from

Ira2 lelql
F (lilOB)
”d 4:: er 2

where r is the distance of the grain from the star. The ratio of the radiative force to
the gravitational force is given by

nazQprh
4ncGM_(§naap,)‘ (11109)

For an AGB star of 1 MG and luminosity 3000 Lo. the value of l" for a grain of radius
0.! p.111, density 1 g cm' 3. and Q” ~ 2 can exceed [04. Because of the large Opacity
of the dust grains to stellar radiation. there is no doubt that the grains will be ejected
by radiation pressure. The only remaining question is whether the dust can effectively
carry the gas with it.
The observed optical depths at l0 ,um of circumstellar envelopes of AGB stars
reach as high as 50. suggesting that the grain density in the circumstellar envelope is
high. This in turn implies that the grains reach a terminal velocity that is much lower
than the velocity of tens of thousands of kilometers per second at which they would
be ejected if they were unhindered. The equation of motion of the grains is therefore
given by the balance between the radiative force on the grain. and the friction induced
by grain—gas collisions. If We define ed as the drift velocity of the grain. then

rrazQ or L -
7? =1": 2 p(r)vd.
2 (15.110)

where p(r) is the density of the gas. The drift vel0city of the grain through the gas is
therefore given by

L
"4: ___Q'" " _ (15.111)
4Jrer1p(r)

Since the grains are slowed down by the gas and momentum is effectively
transferred to the gas through grain-gas and gas—gas collisions. The equation of
motion of the gas becomes

2 L
vfl+l§£+cm _’_'i___’"'
Q" '=o. (15.112)
dr p dr r2 p liner2
Once the equation of state (e.g., assuming adiabatic expansion) is specified. eq. IS. I l2
can be integrated if a is a constant. However. since the grains undergo growth and
 [5.7 Mndsfrom AGB Stars 451

Observer

Figure [5.6
Schematic diagram of an expanding molecular envelope showing the relationship between the
line-of-sight velocity (u,) and the expansion velocity (1:).

reduction in size due to sputtering. the last term may not be directly proportional to
r‘z. A realistic solution involves the assumption of an initial dust condensation radius.
and a formula for grain growth and sputtering (Section 10.10). These parameters
determine whether a transonic solution can be found.

15.7.2 Molecular Line Profile in an Expanding Envelope

One of the most effective probes of the physical conditions of winds of AGB stars
is molecular-line emission. As a result of envelope expansion. the molecular lines
are often much wider than the thermal widths (Au) of the lines. Figure [5.6 Shaw's
a schematic diagram for an expanding envelope. if the expansion velocity is much
greater than Au, then the molecules are not radiatively coupled with molecules in
distant pans of the envelope. The intensity at each line-of-sight velocity 0),) is then
isolated to a pathlength Az(p) that corresponds to At.- centered on 11,. The limits on
A2. are given by Z] and 22.
The antenna temperature (TA) at a given line-of-sight velocity (uz) is the integral
of the product of the telescope beam (G(p). eq. E3. 1 ) with the distribution of radiation
temperature at that velocity. Assuming spherical symmeu'y of the envelope, we see
452 Gas Dynamics. Gravitational Collapse, and Stellar Winds

that the integration is most easin done over the impact parameter p:
Pm
my; = [0 G(P)TR(P. volrwdp. (15.113)

where

c1 _
TR(Po ”2) = '21—; [BU(TI) " Bv(TBG)] [! — e t(p.u,)] (15.114)

and pm is the maximum value of p that can produce a line at velocity 11,. Here TA
refers to the antenna temperature above the off-source antenna temperature.
If We approximate the thermal line profile 4)., by a square of width Au and height
11A 1). then the optical depth along the line of sight at velocity u, is

1:
r(p. vz) =f aunflr) d2. (15.115)
21

where in; (r) is the number density of the molecule in the lower state at radius r. For
a velocin field 120') = ugh/Rye, the line-of—sight velocin at (p. z) is given by

u, = vow/R)” ( E)
r
(15.115)

where R is the radius of the molecular envelope. Using eq. l5.1 l6. eq. 15.115 can be
tmnsfonned from a line-of-sight integration to an. integral over radial distance

t'(p. I12) =f lentil-(fil— (15.117)

rl

For a uniformly expanding envelope (:1 = constant)

vz=uEr (15.113)

p = rt/l — (vz/v)2 (15.119)

A”
Az = amt/dz 5 - (u,/u)]2-1"? .
= mun ( 15.120)

Assuming uniform excitation throughout the envelope (T: = constant). eq.

[5.] 13 can be integrated in the optically thick case (r —> oo). yielding

7:40;) 2 TO [I _7 e—Ilnfllll- (viii-)ZIRIIBI] ‘ (1512”

where
C!
r =——— [BATH ~ B.,(Tno)]. (15.122)
° 21w2
 15.7 Wmdsfrom AGE Stars 453

'

Illljllllllllllllll
4 —' ‘ 0.22

I‘l'l'lfil'l‘l'l'l
0.20
0.18
0.]6
- - 0.14
TA 00

731 IO
0.12
J
M

U
I

0.10
i i 0.03

0.04

41.1.1
0.02
L
Q

.0
8
I

lltllll J_lll_ll
40 o to —10 o 10
v: (km/s) V. (kmls)
Figure 15.7
Theoretical profile for molecular emission in a uniformly expanding envelope. Lefi: optically
thick case. Right: optically thin case when the molecular envelope has the same size as the
telescope beam.

Figure 15.7 plots the profile of an optically thick line using eq. 15.l21 for the
case when Ilte beam and source size are the same (3 = R). At the center of the profile
(111 = 0). TA = To. The excitation temperature can therefore be directly measured if
the line is optically thick.
In a stellar wind of constant mass loss rate (M) and constant velocity,

1'
_ _Lf”"_
4rrv(2p.mH)r2

=1 (15.123)
r2.

where u is the mean atomic weight per H atom f is the molecule (e.g.. l3C0) to H2
abundance ratio, and g}- is the fraction of the molecule in the jth rotational state.
Substituting eq. [5.123 into eq. l5.l 17 and integrating, We have

r(p. v.) = M [cos—'(p/r)]r2

p n
u,+Au/2
= “”A [cor' J1 — (v,/u)2] . (15.124)
P u,-Au/2
454 Gas Dynamics. Gravitational Collapse, and Stellar Winds

For an optically thin line (e.g., I3CO). r < 1. eqs. 15.114 and 15.122 give

T307. vi) = Tortp. II.)- (15425)

Substituting eqs. 15.124 and 15.125 into eq. 15.113. we have
4 Fr u,+Av/2 gm

13(1),) = anauToA [cos-1.)] - (Ill/UP] x j; e"‘2 dx. (15.126)

Ul—AU/z

where

2
x = {-41:12 (15.12?)

and

2RJ1 2
rm = an 1"(vz/v)2- (15.123)
Figure 15.7 shows the profile of an optically thin line for B = R. If T, is known
from an optically thick line. then the mass loss rate can be determined from the antenna
temperature of an optically thin line.
Realistically. the molecules are excited by a combination of collisional excitation
and radiative excitation (e.g.. by absorption of dust continuum photons) and the
excitation temperature is unlikely to be uniform throughout the envelope. in this case.
a full radiation transfer calculation is needed. A useful approximation is the Sobolev
approximation where the Doppler shifts introduced by the velocity field far exceed
the local Doppler width created by thermal and microt'urbulent motions (see Section
9.7).

15.8 Systematic Motions in Star Formation Regions

The collapse of protostellar clouds leading to star formation involves systematic gas
motions of both outflow and infall. This process begins with dense (2 105 cut-3)
and cold (5 20 K) clumps of matter called pie-stellar cores. Pre-stellar cores can be
identified as obscured regions in optical and near-infrared maps. or as concentrations
in millimeter continuum (dust) and line (molecular) emission spots. A pre-stellar core
satisfying the Jeans criterion will begin to collapse. and the increased density in the
center leads to the formation of a star. As infall materials continue to accumulate.
they form a rotating accretion disk surrounding the star. The central objects are called
protesters and can be identified as infrared or submm continuum sources. Depending
on orientation, the accretion disk can manifest itself through silicate emission or
absorption features (Section 1 1.2.1). Later. a bipolar outflow emerges from both sides
ofthe accretion disk. and both the infall and outflow materials can be observed through
their respective molecular emissions.
Figure 15.8 shows the spectrum of formaldehyde in a highly embedded young
stellar object [HAS 4 in NGC 1333. A clear inverse P Cygni profile can be seen.
 L18 System“: Motion: in Star Formation Region: 455

ulllulu-l.gur[lvrvlrv
[0
. Hzco 3,, —2,, mill/454A '
E

(h) f HICO 3,. —2" mm 43 _

vb (km r')
Figure [5.8
Spectrum ofthe 3.2 — 2.. msition of HZCO in two inflated continuum peaks in NGC I333
taken at [RAM Plateau dc Bun: Interferometer showing the inverse PCygni profile. The. 113st
line is a model fit (from Di PM et al. 2001. ApJ. 562. 770).
456 Gas Dynamics. Gravitational Collapse. and Stellar Winds

Assuming that the spectrum is a superposition of a broad emission line centered at

the local standard of rest velocity (11.5,) of the cloud and a cooler front layer undergoing
infall, the velocity ofthe blue-shifted absorption feature can be interpreted as the infall
velocity. In the case of IRAS 4, the infall velocities (1)...) of the two continuum
are found to be 0.68 and 0.47 km s‘ '. respectively. The value of the infaJl velocity is
useful because one can derive the mass of cloud from vi" if it represents the velocity
gain of gas free-falling from rest at r = 00 to its present size of rm. For a total energy
of zero. this gives the following expression fer the cloud mass:

M = Ill-“rin-

2G
2 r.
v' I ll '
:12 __1."

As in the case ofstellar winds. the infall rate Min can be derived using the equation
of continuity for a steady flow (eq. 15.l23). For parameters typical of protostellar
clouds. we haw:
2
[0‘5 l) (. "in )( ”in ) M —1 _
M =32 lD‘em—J‘ ”ms—1 oYf . (15130)
m x #(Ofllpc
where y. is the mean moleCular weight of the gas. and rain is the density of the gas
at rm. Combining eqs. l5.l29 and 15.l30, we have an estimate of the accretion time
assuming that the infall rate is a constant:

(um/1.0kms")
1“ = 1.6 x 10"[ ] yr. (15.131)
an coin/0.01 pc)(rti..,/1Cl‘5 cm'3)(p/2.3)mH
The infall velocity can be compared to the typical sound speed in molecular
clouds. From eq. l5.22. we have

a=0.39 Wms'l. (15.132)

V (la/13)
Comparisons between observed infall velocities to the esfimated sound speed in
eq. 15.132 suggest that infalls can also be supersonic in the ISM.

15.9 Summary

In this chapter, we have discuSsed the systematic motions of infall and outflow in
only one dimension. In reality. both phenomena have been observed in nonsphericalll’
symmetric circumstances. Examples include accretion disks. bipolar outflows from
young stellar objects. outflows as a result of rotation and magnetic fields (e.g.. in Be
stars). bipolar and point-symmetric outflows in planetary nebulae, and so on.
 Exercises 457

As illustrated in the star formation scenario. outflows do not necessarily happen in

isolation. The bipolar outflow in a young stellar object can mechanically interact with
the infall material. leading to dynamical situations more complicated than described in
dynamical equations in this chapter. For example. the outflows can create turbulence.
which in turn provitks support against the cloud from further collapse. If the time
scale of the dissipation of turbulence is long, turbulence, rather than thermal energy.
can be the dominant pressure against gravitational collapse.
Shock waves generated by stellar winds may also trigger the onset of star forma-
tion. The observation of short-lived nuclei (e.g.. 4'Ca and 26M) in meteorites imposes
an upper limit of < 106 yr on the time scale of collapse. Since these short-lived nuclei
are unlikely to have been synthesized in the solar system after collapse has begun.
they were probably delivered to the solar system by stellar winds from nearby stars.
A stellar outflow can run into matter in the ISM. or into another earlier outflow.
as in the case of planetary nebulae and supernovae. If the outflows are supersonic.
then such interactions can create shock waves that have dynamical behavior different
from the dynamical phenomena we are accustomed to in our everyday life. The study
of interactions between outflows and their surrounding environment is the subject of
the next chapter.

Further Reading
For a comprehensive coverage of the theories and observations of stellar winds. see
Lamcrs. H. J. G. L. M. and Cassinelli. .l. Introduction to Stellar Winds. Cambridge
University Press (1999).

For a general treatment of gas dynamics, see

Shore. S. N. Arr Intmducriorr to Astmphyrr'cai Hydrodynamics. Academic Press (I992).

Exercises

1. Find numerical solutions to the Lane—Emden equation for n = 0.5. l. 1.0. 1.5. 2.0,
2.5. 3.0. 3.5. 4.0. and 4.5. Determine the values of {I for each casa and find the ratio
of p; to 5.
2. If a particle of mass m is initially at rest at a distance r0 from a mass M >> m.
what is the gravitational free-fall time? Calculate the value of this free-fall time for
M = Me, r0 = lpc.
3. (a) If the Sun is not supported by gas pressure (T + 0). how long does it take for the
Sun to collapse (assuming a uniform density distribution)?
(b) If the gravitational potential energy is the only source of energy for the Sun. how
long can the Sun maintain its present luminosity?
(c) Compare the dynamical time scale frorn (a) with the thermal time scale from (b).
458 Gas Dynamics, Gravitational Collapse. and Stella: Mad:

4. Let us consider a stellar wind that expands at constant velocity u but whose mass loss
rate decreases as a power law of time

1131(1) = Moog/r)“. (1515.1)

where t = to is the time when the ejection begins. From the equation of continuity_
the density profile at time t is given by

M1: — (r — ram]
M". I ) = 4",er (E152)
where r = r0 is the base of the stellar wind. Show that

Mo ”to )a
, I = — .
p(r ) 4m'2u (vt — r + r0 (5113)
Assuming that the absorption coeflicient x is a constant. the radius of the photospbere
(roll at which 1' = 2/3) is given by
2 R0)
-— = trp(r, 0dr. (EISA)
3 rwtt)

where R(t) = r0 + u(t - to) is the outer edge ofthe wind. Show that for a = l. rfl, is
given by the root of this equation:

87m: u (mo) u u
. +—+ln — = +ln —l , E115
3xMolu R R r9110) rphll') ( )

where u = u! + r.
If the mass loss rate decreass exponentially with time

11'1(:)= steam—qr). (1515.6)

show that the density profile is

p(r, t) = flak/”Tr_2e"’/”T, (Eli?)

47w
and the total envelope mass after time t is

Ami) = MDT [1 — 9"]. (1515.11)

. In the early 1970s. UV observations of novae on the Orbiting Astronomical Observa-
tory (GAO-A2) found that the far-UV flux of novac underwent a rapid increase as their
visual brightness decreased. This suggests that the bolomctric luminosity of novae is
approximately constant over several months after outburst and the visual decline of
novae is the result of the shrinking of the photosphere and associated increase in the
efiective temperature.
 Exercises 459

Assuming a constant luminosity (L = 1000 L0), Mo = s x 10—5 MG, yr'. 1: =

1000 km s", to = 0.1 yr. calculate the change in effective temperature as a function
ot'ljme between t = 0 to 100 days for thee: = I using eq. E155.
The visual magnitude is related to effective temperature through the bolometric
correction (BC)

and

so = -4154 + 10103 ref, + (29,000 Km") (515.10)

Calculate the light curve (MV us I) of the nova for the first 10‘.) days after outburst.
. A stellar wind of mass loss rate [0" M0 yr" and terminal velocity 1000 ltm s" is
fully ionized by its central star. Assuming that the wind is composed of pure H and
has an electron temperature of 10‘1 K, calculate the ‘l' = I surface of the wind at 0.],
I. and ID GHL If the wind is cut off at a distance of 1 pc, what would be the effect
on its f—f spectrum?
 16
Interaction between Stars and
the Interstellar Medium

The mass of stars is not conserved from birth to death. AlIhOugh the initial mass of
stars can range from less than 1 Mn to over 50 Mg, stellar remnants (white dwarfs.
neutron stars. and black holes) have masses ranging from 0.5 to a few Mr: . The
difference between the initial and final masses is ejected into the [SM during a star's
lifetime. Such ejecta inject a large amount of mass. momentum, and energy into the
ISM and can cause major perturbations in the structure of the ISM.
Low- and intermediate-mass stars (initial mass 5 8 Mg, Secu'on 1.2) return most
of their mass to the ISM in the form of stellar winds. and only a small fraction of the
original mass of these stars ends up as stellar remnants in the form of white dwarfs with
masses between 0.5 and L4 M19. For high-mass stars(> 8 M5,), the amount of energy
injected in the form of stellar winds during the main sequence and Wolf—Rayet stages
is roughly comparable to that ejected during the supernova stage. Although stellar
winds are extensions of the stellar atmosphere and can be considered as a strictly
stellar phenomenon. their mechanical influence on the ISM suggests that they cannot
be considered as events isolated from the overall structure of the ISM.

16.1 Supersonic Dynamics

In the previous chapter on stellar winds. we saw that radiation pressure from Stars can
drive gas into highly supersonic speeds. Other examples of supersonic motion in the
ISM include planetary nebulae expansion. nova ejections. and supernova explosions.
As these high-speed gases run into the general ISM, they cause a disturbance to the
ISM. Generally, when a stationary gas is disturbed, the resultant changes in velocity.
density. pressure. and temperature are communicated downstream at the sound speed
(eq. 15.20). But for a supersonic gas. the motion itself is faster than the speed of
communication, and instead of a smooth transition. these physical quantities undergo
a sudden change in values over a small distance. This phenomenon is referred to as a
shock.
We define the shock front as the region over which the velocity. density. and
pressure of the gas undergo sudden changes. If we approximate the shock from as

461
462 Interaction benveen Stars and the Interstellar Mediwn

Shock front
P.
i
' 4——
u.p.P I
.0. - a”

Shoelredgas Unshackedgas

<—
............... u. 90
:. ....... 5 ....... ..
I

Figure 16.1
A schematic diagram illustrating the sudden change in velocity. density. and pressure afier the
passage of a shock (in shock-fitted coordinates).

a surface of zero thickness at position x,. then the velocity. density. and pressure of
the gas change from no to 1).. p0 to p.. and P0 to P] from J: < .r, to: > x, discretely
(Fig. 16.1). Let us consider a shock propagating with velocity u, into a gas that is
previously at rest. In the frame of reference of the shock, the gas is approaching at a
speed of —v,. If we define the speed of the gas in the frame of reference of the shock
as u. then u = v —- u, and the speed ofthe gas in front (no) and behind (at) are -—u,
and v. — up respectively. Since the mass flux entering the shock from in front must
be the same as the mass flux leaving the shock. we have

Pouo=Ptur (15-1)

Similarly. the change in the momentum flux ((puJu) must be balanced by the ptessure
change across the from.

P0 + port; = Pt + pluf. (I62)

For an ideal gas. the energy density is the sum of the kinetic energy ipu’ and
internal (thermal) energy U = 11.0. The difference between the rate of energy entering
and leaving the shock is the work done by the gas as a result of the pressuredifieremc
across the shock;

I l
M] (EPIU? + 01) — Ho (Egon: + U0) = Polio — Plul' (16-3)
 16. I Supersonic Dynamics 463

Substituting eqs. 15.16 and 16.1 into eq. 16.3. we have

1 2+
_ V P°—l 2+—"—&.
_ _ (l6.4)
2"0 y—lpo 2'" r-lm
From eqs. 16.]. 16.2. and 16.4, we should be able to derive the changes pI/po. 1.11[1.10.
and P1]P0 across the shock. If we define a dimensionless scalar variable Mo 5 [Mal/00
and make use of eq. 15.21. we have
u!
P0 = . (16.5)
VME
In the fixed frame of reference (e.g.. relative to a star), 119 = -v,. M0 is therefore the
ratio of the shock speed over the sound speed. and is called the Mach number.
Substituting eqs. 16.]. 16.2. and 16.5 into eq. 16.4, we have

at: +11: — c=0. (16.6)

where

J‘=1"’0/1|'91
_'__Y_
“—2 y—l

b=_l_ ' 2
r-1 (r—IWD
1
=_+
1 _
c 2 (y—1)Mg ( 15.7 )
The two roots of this quadratic equation represent the densities on either side of the
shock:

__ 1 141-1
A) [$5 + (y—IJMDI] i Moity—I) {[6 B)
—- = 2 . t
P) 1— 7E]

The root with the negative sign gives back the pie-shock density (p0 = p1). whereas
the root with the positive sign gives

1 M’-
Q =_______(”+
) 0 2 . (16.9)
Po (Y+1)+(Y-1)(Mo—1)
For a strong shock (MD —> on),

”1 2 Lil. (16.10)
464 Interaction between Stars and the Imem’eflar Medium

If the shock is adiabatic (y = 5/3). the degree of compression cannot exceed 4, no

matter how strong the shock is. An adiabatic gas. 110: being able to radiate away the
excess energy. will have all the kinetic energy changed into internal energy, Which
resists further compression.
For an isothermal shock (y = l) where all excess energy is effectively radiated
away. no such finite limit exists and pI/po —> 00 as M, —> on.
From eqs. 16.1 and eq. 16.9. we have the change of gas velocity across the shoclc

£9_ (1’+DM§' 16
111 {y+1)+(y—1)(Mg—1)' ("1)
Transfomfing eq. 16.11 back to the stellar frame of reference using no = -1), and
111 = 1.11 — 11,. we have

- v, _ (y +0143
v. —- u. (y + 1)+ (y — 11mg ~ 1)
u, = 11,. (16.12)
y+l

For a strong adiabatic shock. eq. 16.11 gives 110/11. —> 4. From eq. 16.12. the shocked
gas is accelerated to 3/4 of the shock speed. For an isothermal shock (y = 1), eq. 16.1 1
gives

110-4143;... (16.13)

In the stellar frame of reference

—u, = M3011 — 11,)

6.: (1— 15-5)!)r (16.14)

0

For a strong shock, the shocked gas is accelerated to the speed of the shock (I), = 11,).
We can substitute the results from eqs. 16.5. 16.9. and 16.11 back to eq. 16.2 to
obtain the jump in pressure:

f_I_ 21’ Mg V“_ (16.15)

Po Y+1 y+1

Eqs. 16.9, 16.11, and 16.15 are together refined to as the jump conditions across a
shock.
Using the ideal gas law

p .__ L"! (16.16)

 16.1 Supersonic Dynmnics 465

5m 1 1 I I I

Tm

Figure l6.2
A plot of the jump in temperature after the passage of a shock of Mach number M0 for y ; 5/3
and 7/3.

and eqs. 16.9 and 16.15. We have

(M02_ 1)]
5 =10» + 1) + 2th3 — mm» +1)+(y -1) - (16.17)
T“ (r + 112513
An illustration of the temperature jump as a function of MD is given in Figure 16.2.
From eq. 16.15. we can see dial for a strong shock. Pl >> Po and the Po term in
eq. 16.2 can be omitted. Making use of the strong shock approximation (eq. 16.10)
and the equation of continuity (eq. 16.1). we have

P = 2
-—- u2. (16.18)
' (r + 1) p0 D
For an adiabatic gas (y = 5/3),

3 2
P, -.= 21:10:10. (16.19)

Substituting eq. 16.18 into the ideal gas law (eq. 16.16). we have

T = 2(r-l)
__ Min 2 '
__. [520
' [(y+ 112] k u” ( )
466 Interaction between Stars and the Interstellar Medium

For a shock velocity of 1000 kin/s. the post-shock gas can be heated up to over 10
million degrees. Shocks therefore represent an effective heating mechanism of the
ISM. In the rest of this chapter. we will consider three examples of the interactions
between stellar ejecta and the ISM. and how these interactions can result in dynamjcal
expansion. compression. and heating of the ISM.

16.2 Supernova Remnants

A supernova explosion is the result of the gravitational collapse of the stellar core,
resulting in a release of a large amount of energyr accompanied by the ejection of the
stellar enveloPe (~ 1M0) at high speed (~ 10" km 5“). When this ejecta encounters
the interstellar medium. a shock wave will form. As the shock passes, the interstellar
gas will be heated and accelerated. fenning a supernova remnant. When the amount
of shocked interstellar gas exceeds the mass of the ejects. the mass of the ejects can
be ignored and the expansion of the supernova remnant can be treated as an explosion
with a release of a finite amount of energy E. at t = 0.
Since the velocity of the ejecta is much higher than the sound speed in the ISM,
we can make use of the strong shock approximation (eq. 16.10). Using tags. [5.l6,
16.10. 16.18. and no = —u,. we can derive the internal energy per unit mass for the
shocked gas to be

“ll = —— 2
(y +1)2"r2. .
(1621)

For an adiabatic gas

9 2
11 = 351:3. ([622)

The kinetic energy per unit mass of the shocked gas is

l
0' = inf. (16.23)

Making use of eq. 16.12, we can express 9' in terms of the shock speed:

9 2
T = -—-U . (1624)
32 "
Provided that most of the mass in the supernova remnant is made up of shocked
interstellar gas and the mass of the stellar ejects can be neglected. the total energy of
the expanding remnant is

E, = gamma + 'tl). (16.25)

 I62 Supernova Remnants 461

where R is the radius of the shock front at time 1. Writing 11, as Ii and making use of
eqs. [6.22 and 16.24, we have

4 3 18) -2
E r =-J'I'R
3 —
90(32 R

= inkslizpo. (16.26)

Assuming negligible radiation losses. we can regard the supernova as being in

adiabatic expansion and E,- can be equated to E.. With the initial condition R(0) = 0.
the equation of motion

191'?2 = $0 (16.27)

can be integrated to give

R = (3)115 (film ‘2” (16.23)

= 5.6 (%}$)us (”WWI/5 pc. (16.29)

The expansion velocity can be found by taking the first derivative of eq. 16.23:
_ 1/5 us
R = 3 (E) (5) 1-3/5 (16.30)
5 31! pg
1/5
E./IO5l erg
: 2200 ( /I _,) (1/103 er'i‘V5 kins-1. (16.31)
min Cm
Although the expansion is impeded by a larger initial density of the ISM, a higher
density will lead to a higher mass in the supernova remnant. The amount of shocked
interstellar gas at time t is given by

M: = girflapo (16.32)

:13 E. 3/5 “"0 2/5 3 6/5 M . 16.33

(l05'e1g) (lam—3) (103 yr) 0 ( )
We can see that this mass becomes much greater than the ejected mass at large t.
therefore the assumption that we made in eq. 16.25 is justified.
In an ideal gas. each particle contributes equally to the pressure. Assuming that
the remnant is totally ionized. we see that the internal energy of the shocked gas is

11:; RT .
{16.34)
2113171“
468 Interaction between Stars and the interstellar Medium

where ,u.’ 20.6 is the mean atomic weight per particle. Equating eq. 16.34 With
eq. 16.22. we have

_ 3 u’mHRZ
— 16 I: (16.35)
E_/105'erg)2’5 _
=1 01 u. (“no/1cm4
_— (1/ 10’ yr) w K . (16.36)

We note that eq. 16.35 is the same expression as eq. 16.20. For E, = 1052 erg,
no: lam—3.11.: l.andp.’=0.6. then r~4 x106Katt=lU4yn

16.2.1 Momentum-Conserving Phase

As the shock speed decreases with time. the temperature of the shocked gas will
decrease. Eventually. the gas temperature is low enough for recombination of metal
ions to occur, resulting in the availability of many lines for cooling (Section 6.5).
This cooling causes the temperature immediately behind the shock front to drop even
further. Pressured by the hot gas. the cooled gas will be compressed. forming a high-
dcnsity shell. The high density ftu'ther accelerates the cooling and a thin shell of cool
gas will form. \Vtth efficient radiative cooling. the expansion of the supernova can no
longer be considered adiabatic and the equation of motion will eventually be governed
by the conservation of momentum.
Assuming that the momentum-conserving phase begins at t = to and the momen-
tum of the shell, pa := Mgr. remains constant hereafter with the value of

500 = (gflRgpo) 1'10, (16.37)

we have the equation of motion after to.

4517R 3poR- = pa. (16.38)

Equation 16.38 can be integrated with respect to time to give

134 = ___3PO , 4. c. (16.39)

4 411,00

where
1 .
c = 2113 — 112311010 (16.40)
after applying the initial condition R = R0. R = R0 at to. The solutions tothe equation
of motion are
- 1,14
4R 1— (16.41)
R = 11., [1+ —0(Ra 10)]
 16.2 Supernova Remnants 469

it = R0 [1+ 43‘2 (r — gym (16.42)

R0

Fort >>to + Ro/Ro

R o: 11/4 (16.43)
ft 6:14“. (16.44)
By comparing eqs. 16.30 and 16.44 we can sec that the expansion slows down faster
in the momentum-conserving phase than in the energy-conserving phase.
The fraction of energy (a) going into shell expansion during the momentum-
conserving phase can be obtained by comparing the kinetic energy of the shell,

1 4 3 -2
E K =— - R Po) R
2(3tr ( 16.45 )

= impure, (16.46)
with the amount of energy E, released in the explosion:

“6.47)

Substituting eqs. 16.41 and 16.42 into eq. 16.47 and assuming I >>10 + Ro/Ro. we
have
1,-4 flémfl
a m Lm . Jis
gur—
(16.48)
6 E...

Substituting the solutions of the equation of motion (eqs. 16.23 and 16.30) for t = to
into eq. 16.48. we have
”4 5,14 .

”(47%) (E) "0/0""

a 0.625(10/19", (16.49)
for I >> to + R0/ R0. As the supemova remnant evolves, the energy efficiency de-
creases. At t = 100:0. the kinetic energy of the shell represents only 25E- of the initial
energy of explosion.
Although the example above gives a simple illustration of supersonic dynamics, it
is not a realistic treatment of the expansion of all supernova remnants. We now know.
forexample. that Type 11 supernovae do notexplode in a vacuum. but in a circumstellar
470 Interaction between Star: and the Interstellar Medium

medium created by their progenitor red supergiant. From HST observations of SN

I987a, we know that this circumstellar medium is not spherically symmetric, and lhe
expansion of the supernova remnant Shauld be treated with a 2-D analysis.

16.3 Interstellar Bubbles

Let us consider the case where a star is ejecting mass at a rate of in in the form
of a steady stellar wind with velocity u. When this stellar wind runs into the ISM,
assumed to censist of pure H of density p0 and initially at rest, the interstellar gas win
be swept up by the wind forming a shell. Since there are three mass components (the
undisturbed interstellar gas. the fast wind, and the swept-up shell) in the system. have
shack fronts will be formed. An outer shock propagates into the [SM and the inner
shock toward the star. Due to the high velocity of the central star wind. the Mach
number of the inner shock is Very high and the post-shock region will have a very
high temperature. As a result the inner shock is likely to be adiabatic because of the
low efficiency in radiative cooling at high temperatures. This high-temperature region
is referred to as a "bubble" (Fig. 16.3).
If We assume the expansion velocity of the shell is moderate (which can be
continued later by the solutions). the temperature in the post~shock region is likely
to be low enough to allow for the existence of metal ions. allowing for forbidden line
cooling. Therefore. the outer shock can be treated as isothermal. Since the density
jump across an isothermal shock is proportional to the square of the Mach number
and not limited to a maximum value of 4 as in an adiabatic shock. the shell density
can be very high and the thickness of the shell can be considered to be small.

Figure 163
An example of a wind-blown bubble in the H [I region 305.2+00.2. This 5.3mm image was
obtained by the Infrared Array Camera of the Spritzer Space Telescope during the GUMPSE
survey.
 I63 Interstellar Bubble: 471

Contact discontinuity

Shocked _
stellar wind Egg?
bubble gas (p0)
(Po- 1i» Pb)

" I

L Swept-up shell (p’)

Figure 16.4
Schematic diagram of the interstellar bubbles problem.

The problem can be further simplified by the introduction ofa contact discontinu-
ity separating the shocked stellar wind and the shocked interstellar gas (see Fig. 16.4).
It is assumed that no gas can cross this discontinuity and therefore the temperature
and the density of the gas can take on independent values on either side of the dis-
continuity. However, the pressure is assumed to remain unchanged and the dynamics
of the two sides is therefore coupled. 111is allows the two shocks to be considered
separately.
The mass of the shell. made up entirely of swept-up gas, is given by

M, = (3:133) p0. (16.50)

Under the assumption above. the only force driving the expansion of the shell is
pressure of the shocked stellar wind. The equation of motion of the shell is therefore

d (3::
dt
-— 4- R 3 poll)
' =4at R 2 P , ( 16.51 )
472 Interaction between Star:- and the Interstellar Medium

where 47! R219 is the force exerted on the shell by the bubble. The thermal energy par
volume for the bubble is

U = —nkT. (1652)

Using the ideal gas law. we obtain

MIN
C-

7“
(16.53)

II
If there are no radiative losses, the only terms in the energy equation are the change in
the thermal energy of the bubble, mechanical energy input by the wind (E = éfitu?)
and the work done as the result of the expansion of the shell:

1 [3:113 (319)] =15" — P1 (in?)

:1: 3 2 d: 3

22:21:03?) :13" — EnPimJ)

3 d:

21! 11315 + 21(3R2R)P = E — gnPGRZR). (16.54)

From eq. l6.5l, we have

411R2P = 21113390]? + 4nR2p01't2

P = gpuit'it + port? (16.55)

and

p = 31p.) 1111 +§p01111 mm

p= gm. 1111 + giant-111'. (16.56)
 hi3 Interstellar Bubbles 473

Substituting eqs. 16.55 and 16.56 into eq. 16.54. we have

21,)!} ($10033? + EpoRli) + 61rR2R (gpoRli + pol?!) = E — 4xR2R (ii-Po“? + POI-ll)

12411 + 71131111 + 31131111“ + 9111113 + 21131111 + 612213 = i

ano

R‘Vlt' + 12R§R3+ 15192113: 315—. (16.57)

“Po
This is a third-order nonlinear inhomogeneous differential equation whose homoge-
nous and particular solutions correspond to the transient and steady-state solutions.
respecdvely. If we are interested only in the asymptotic behavior of the system at large
1, we need only find a particular solution. A possible guess is that the solution has the
form R = At“. where A and a are constants. Substituting into eq. 16.57. we have

A5 [a (a —1)(a — 2) + 12112 (a — 1) + 1563] :5“ = 35. (16.58)

27mg

For E = constant. the time dependenCe on the LHS must vanish, implying that
So — 3 = 0. or at = 3/5. Substituting this value into eq. 16.58 and solving for A. we
have

2 i 13* i
“(2)
1541!
H
pg
. (.659)
A solution of eq. 16.57 is therefore

_ 125 i (p—o)
R_(T5?J;)
11: 5!I. (16.60)

The eJtpansion of the shell is given by

R = Atria"

=3(£)
1 5- i 1-5. (16.61)
5 154:: p0

Since the rate of energy input into the system by the stellar wind is a constant and the
shell mass is increasing with time. the rate of expansion has to slow down with time.
If we express eqs. 16.60 and 16.61 in typical observed parameters. we have

' —l i
11:21 (m
M [lam—3 ) (t/IOGyr)§pc (16.62)
D
474 Interaction between Star: and the Interstellar Medium

. _I l
R=rs (%) (t/lO‘erilt-mS‘I- (16.63)

Equations 16.62 and 16.63 describe the asymptotic behavior of the expansion of an
interstellar bubble.

16.3.1 Temperature and Density of a Bubble

if there is no mass diffusion across the contact discontinuity. the mass in the bubble is
the total of all masses ejected by the stellar wind. The density in the bubble is therefore

__ hit 16

Applying the ideal gas law. we see that the temperature in the bubble is

Prim"
Tb = ————.
put ( 16.65 )

Substituting the dynamical solutions (eqs. 16.60 and 16.61) into eq. 16.55. we have

-—
7 ——-—
E- l t ‘3.4
125 i (‘00)
P = 2511)::(154fl) —— .
(1666)

Substituting eqs. 16.60 and 16.66 into eqs. 16.64 and 16.65, we have

3
= __ 154:: 3 _,-
p0 i ' ‘3
t
9" 4x(125)(£)"" ( 16.67 )
and

5 113mm:2
T = ———. 16.68
” 33 r ( )
For v = 2000 runs—1, we find that 1,, =4.4 x 107 1a m such high temperatures,
almost all atoms are ionized. so radiative cooling is not reflective. In practice. thermal
conduction across the inner boundary of the shell causes gas to evaporate from the
shell to the bubble. where it mixes with the shocked stellar wind. Although the m
of the evaporated gas is small compared to the mass of the swept-up shell, it may
be significant compared to the mass ejected by the stellar wind. This increase in the
bubble's mass and density will cause the temperature of the bubble to drop with time.
When this temperature is low enough (e.g.. < 10'6 K), radiative losses will become an
important factor. which eventually leads to the breakdown of the energy-conschiflfl
approximation.
 16.3 Interstellar Bubbles 475

16.3.2 Energy Efficiency of Bubble Expansion

Provided that there is no loss of energy due to radiation, the theoretical efficiency of
the transfer of energy from the stellar wind to shell expansion can be calculated. The
kinetic energy of the swept-up shell is

15,( = % (gnlflpo) R2. (16.69)

Substituting eqs. 16.60 and 16.61 into eq. 16.69, we have

new) (fl)
3 5 154::

=—Er. (16.70)

Therefore z 20% of the wind energy is channeled to kinetic energy of the swept-
up shell. The remaining energy is convened to internal energy of the bubble. This
theoretical efficiency can be compared with the observed efficiency based on the
observed parameters (MI. E) of the shell and the expected parameters (in. v) of the
wind.

16.3.3 Density of the Swept-Up Shell

If the outer shock is an isothermal shock (y = l), the density of the swept-up shell
(p,), given by eq. 16.9. becomes

p, = M390
. 2
=(5) p0. (term
‘10

Since the sound speed in an isothermal shock is a constant. we have from eqs. 16.61
and 16.71 the following time dependence for the shell density:

p, o: rt (16.72)
476 Interaction between Star: and the Interstellar Medium

Since the shell is entirely made up of swept-up gas, the thickness of the she]:
(AR) is given by

47rR2ARp, = 217123730

AR __ i an 2
7—5 F - (16.73)

For a stellar wind of 77': = ID“ Mo yr"1 and v = 20001011 5" running into
the ISM with a density of no = I cm‘3 and y. = 1.4, we have from eq. 16.61 that
R = 40 km s"I at r = l05 yr. Comparing with the sound speed (on) of ~ lOkms-l
at T = 10" K (eq. 15.22. assuming y = 5/3). we have a Mach number (Mo) of ~ 4
for the outer shock. The shell thickness from eq. [6.73 is AR] R z 0.02. Therefore,
the thin shell approximation is justified, at least during the early stages of the bubble
expansion. Substituting eq. 16.61 into eq. l6.73. we can see that the shell thickens
with time as AR/R 0: r4”.
From eq. 16.71. the density of the shell is 16 cm" at r = 10’ yr. In comparison.
the density of the bubble is 2 x 10‘3 cm'3 from eq. l6.64. The shell density is
therefore ~ 7800 times the density in the bubble.
The swept—up shell will be totally ionized as long as the number of Lyman
continuum photons output from the central star (Q. eq. 4.49) is larger than the critical
value given by eq. 4.52:

Q = 47r RZARxenfag. (16-74)

where x, = .m/riI (Section 6.3). Making use of eqs. 16.7l and I633, we have

Q, = fgnfiwonjofl. (16.75)
From eqs. 16.71. 16.60. and 16.6]. we have

eeexsxzfli)(sw-
As more and more interstellar gas is swept up, Qc increases linearly with time.
Eventually Q. will exceed the stellar Lyman continuum output. and the gas outside
the shell will no longer be ionized. From eq. l6.76. this transition occurs at

2
r: (E) MH—Q. (16.77)
30 81',nt

Assuming that the shell has a temperature of T = 10‘ K. on will have a value of
2.59 x 10‘13cm3s" (Section 4.5) and the sound speed is l0 luns". For Q =
1043 s". x, = 1.17. p. = 1.4,no = um”, and the same wind parameters as beforc.
the recombination of the shell occurs at r = 5 x 105 yr. The shell radius at that poifll
is 13 pc and the shell is expanding at 21 km s'l.
 16.4 Interacting Stellar Winds 4‘77

15.4 Interacting Stellar Winds

The interacting stellar wind model describes the dynamical interaction between two
successive stellar winds. This mechanism was first proposed to explain the origin
of planetary nebulae and has since been applied to a variety of other astrophysical
phenomena, including ring nebulae around massive stars (WR stars. luminous blue
variables and blue supergiants). supernovae, young star outflows. relativistic jets in
active galactic nuclei. as well as galactic superbubbles. In contrast to the interstellar
bubble case where a stellar wind runs into a stationary. constant density medium. the
interacting winds process considers the possibility that both media have a density
and velocity structure. In the basic scenario, we consider a steady stellar wind with
constant mass loss rate and velocity interacting with an earlier ejected stellar wind
also with a similar steady wind, both originating from the same star.
In this one-dimensional case. we can define r = 0 as the position of the star.
which has been ejecting a steady stellar wind of mass loss rate M and velocity V for
an extended period of time. At time t = 0. the stellar wind transforms to a faster wind
of mass loss rate ti: and velocity v. For easy reference, we will refer to the earlier wind
as the slow wind and the later-developed wind as the fast wind. The density structures
of respective stellar winds are given by the equatiou of continuity:

r =
p() 411'r2V

p'fl’) = (16.73)
4n r21).

Since V and u are constants. both density profiles have inverse-square distance
dependencies. Assuming that v 1-» V, the fast wind will soon catch up with the slow
wind, and the subsequent dynamical interaction and the development of new density
and velocity structures is the topic of this section.

16.4.1 Momentum—Conserving Case

ASSuming that the collision between the fan and slow wind is inelastic. the fast wind
will begin to sweep up material in the slow wind to form a shell. For the time being,
we will assume that this shell is thin with a thickness much smaller than its radius R5.
The amount of mass in the swept-up shell (M,) at time t is given by the sum of the
total amount of mass in the slow wind between radius Vt and R,, plus the amount of
mass in the fast wind between radius R, and or. From the density profiles (eq. 16.73).
we have

ll, ' ur -
M, = Edr + f 3dr
Vt V R I)

—
All _
tit -
_ —
— (— u) R, (M —
”1):,
I
(16 .7 9)
478 Interaction between Star: and the Interstellar Medium

where we have assumed lhat the stellar radius is much smaller than Vt and ut. From
the conservation of momentum. the equation of motion of the shell can be written as

MJR} = $0: — Rs): — g0? - IL):- (16.80)

By defining the following constantsa = M/V - nit/u, fl = M — 51,8 = n'w —- HV,
we can rewrite eq. [6.30 as

M,R,=—aR§+2flR,+8. ('53!)

Introducing the variable

M
y = —’
a
06.82)

y — R: _ gt
a

y = k: _ E

55: R}. (16.83)

Equation 16.31 can be written as

.. 52 .2 5 (16.84}
yy=-3-y
a
+--
a

Defining the constant I; as

were
£49.- .0»; W (16.85)
Va (ti/v — mu)?
eq. [6.34 can be written as

d - = 1: . (16.86)
("(17)

Equation 16.86 can be integrated to give

y=:|:‘f{t1+clt+c2, (16.87)
 16.4 Interacting Stellar Wind's 479

where c. and (:2 are integration constants. Since

R,=y+£t, (16.38)
0!

we have

R5: EfiJClz'i'C'f-i'ta. (16.39)

a

The velocity at any given lime l’ is

R, =
g+ ; +c1/2t (16.90)
a «I; + cl/r +c2/r2'
The integration constants c, and c; are to be determined from initial conditions R, (0)
and 85(0). At large I, eq. 16.90 reduces to

Rs“ =00) = E :1: J?

a

_ (M — n'.) a: (u - V)‘/Mm/uv
(16.91)
M/V‘ri’l/v
We can see that only the + case represents a physically interesting solution. The
terminal velocity

(M — at) + (v — V)\/Mrii/UV
R = = . (I692)
"U m) M/v—m/u
can also be found by setting the left-hand side of eq. 16.80 to zero.
Let us apply the solutions above to the dynamical evolution of planetary nebulae.
For several hundred thousand years, an AGE! star has been ejecting a steady stellar
wind with M x: IO‘5 Mo yr" and V = 10km 3“. When this wind has nearly
depleted the entire hydrogen envelope of the AGB star. the hot core is exposed and
begins to eject a faster wind with rit = 10‘8 MG yr". and u = 2000 km s". From
eq. [6.79 a shell of mass M. 2 0.04 Mo will form after 10" yr. With these wind
parameters. eq. 16.90 shows that the shell accelerates quickly and the expansion
has already entered the constant expansion phase at t: 10" yr, with a terminal
velocity V, = Ii: = 14 km s ‘ given by eq. 16.92. Since these values are comparable
to the observed masses and expansion velocities of planetary nebulae. it suggests that
planetary nebulae can be fonned by the interacting winds process in about 10" yr.

16.4.2 Energy-Conserving Case

In the momentum-conserving cases we assume that all the excess energy of the fast
wind is radiated away. Since the observed velocities of winds from central stars of
planetary nebulae are much higher than the sound speed. the shocks generated can
create very high-temperature gas in the post-shock region if cooling is not efficient.
480 Interaction benveen Stars and the Interstellar Medium

Outer shock

PN halo
(dust and molecular emission)

“a
Inner shock

p
au‘
Fast wind f x

"'-_-.-_-o-"
U -' 2000 ms \\
‘ Hot bubble

1
A03 wind
V- 10 Ion/s

..,
EN shell
R, ~ 25 kmls
(recombination
and forbidden lines:
free—free emission) \J . \

Figure 16.5
Schematic diagram of the interacting winds process in planetary nebulae. The radiation
mechanisms in the different mass components are identified.

pran of the energy of the fast wind is nansfonned into thermal energy, then thermal
pressure will provide additional acceleration to the nebular shell.
As in the intersmllar bubble case, the energy-conserving case of interacting winds
can be approximated by two shocks. an adiabatic shock propagating toward the star
and an outer shock that is isothermal. In order to simplify the problem. a contact
discontinuity is assumed to separate the hot bubble and the swept-up shell across
which no gas or heat passes. The gas pressure is assumed to be unchanged across the
contact discontinuity but the temperature and density take on discontinuous values.
Thus the shell is made up only of swept—up slow wind, and gas in the “hot bubble”
is all from the central star wind. A schematic diagram of the [SW model is shown in
Figure 16.5.
From the conservation of mass, the rate at which mass is being swept up is
given by

% = 4nr2p(r)(li‘, - V). (1693)

where p(r) = M] (4Jrr2V) is the density profile of the slow wind. Therefore the shell
mass at time: is given by

Ms“) = gut, — Vt). (15.94)

 16.4 lruemcting Stellar Wind: 481

At a given time, the swept-up shell is pushed by the thermal pressure (P) of the
"hot bubble" and impeded by the remnant of the slow wind. Since the momentum
flux from the slow wind is d—glull, -- V), the equation of motion for the shell is

Mj, = 4:: REP -[1v'1,(1i, — V)]. (16.95)

Using eq. 16.94, we can write eq. I695 as

M,ii, = 47mg)" — gut, — V)’. (16.96)

Assuming no energy exchange (the adiabatic approximation), we note that the total
energy input into the bubble from the fast wind (zine?) must be balanced by the
change in the internal energy in the bubble and the work done due to expansion:

i [”2533 (5)] =1,;,.,? -4JrR2Pfl. (16.97)

dt 3 2 2 ' d:

From eq. 16.96, the pressure in the bubble is

1 M d2 2
=———— R —Vt . 16.98
Bung v dt2( ‘ ) ( )
and eq. 16.97 can be written as

d[R3 (211R2 P)]_"'

R—zd— — —.”2 (16.99)
Substituting eq. I6.93 into eq. [6.99, we have

M d 2 112
— R— V: _v' [6.100
”Eva—1PM
’dt2( )]=m2 ( )
This inhomogeneOus nonlinear differential equation can be solved numerically
to give R, as a function of time. However. if we are interested only in the steady-state
solution, a similarity solution can be found by assuming that

R,ott". (16.101)
Substituting eq. 16.101 inlo eq. 16.100 and requiring all team in the equation to have
the same I dependence. we find a = l and

R, = v,:, (16.102)
where V, = R, = constant is the solution to the following cubic algebraic equation:

M
(7)1/3— . + Mvv,
2va - 1 .
= imuz. (16.103)
482 Interaction between Stars and the Interstellar Medium

Substituting eq. 16.102 into eqs. 16.94 we have the result that the shell mass
increases linearly with time:

. v
Ms= M (7‘ - I) 1- (16.104)

Since it, = 0. we have from eq. [6.96

4n vfrzp = %(V, — 1/)2

WIN
EV, . ( 16 .105)
after making use of eq. 16.103. Since V, is constant. the pressure in the bubble is
found to be decreasing with inverse-squared time:

inn: 2 —2
1 (16.106)
6n V33

Using typical observed values for the two winds: M ~ 10‘5 Mo yr‘l, V ~ 101cm s“,
:11 ~ 10-51140 yr".andv ~2000krn s",wehave v, ~ 31m 5" and M,~0.2Mo
after 10“ yr. As expected, these values are higher than the corresponding values found
in the momentum-conserving case (Section 16.4.1).
Since the sound speed in the shocked fast wind (the bubble) is high. the pressure
everywhere in the bubble will be quickly equalized and we can assume that the bubble
is isobaric. The average density in the bubble is
tt'tt
Pb = W. (16.10?)

Applying the pressure jump condition across the inner shock (eq. 16.18). we have

= 316,62, (16.100)
4

where
n'r
= (16.109)
.0. 411er
is the density of the unshocked wind inside the inner shock. The location of the inner
shock (11.) can be found by substituting eq. 16.106 into eq. 16.103:

10,: 3(&)12,_ (16.110)

4 v

For 0 = 2000 kms" and V, = 31 kms'l. we get R1~ 0.19 R... Since (IQ/R.)3 '—"'
0.006. these results suggest that 99% of the volume interior to the shell is shocked-
 16.4 Interacting Stellar Winds 483

Combining eqs. 16.106 and 16.107 and using the ideal gas law as the equation of
state. we find that the temperature in the bubble is

'm 112
T=F_H_
9k . (16.111)

where ,u.’ is the mean atomic weight per particle. For it = 0.6 and u = 2000 km s".
the temperature of the shocked gas is 3 x 107 K.
The efficiency of the interacting winds mechanism can be determined by com-
paring the ratios of the energy and momentum of the shell to those of the central star
wind. The energy efficiency 5 can be defined as
l 2
e ___ EMSVs
. ([6,112)
in")?!

In the case that the mechanical energy of the central star wind greatly exceeds that of
the AGB wind. eq. 16.103 can be reduced to

-2 l
v,=('"3"MV) . (16.113)

Substituting eqs. 16.104 and 16.113 into eq. 16.112. we have

p—a

e~ -. (16.114)
(4-!

The momenmm efficiency can be defined as

II: Ms V: “6.115)
rim: I
Substituting eqs. 16.104 and 16.113 into eq. 16.115. we have

- i
nz—lz-(fl)
33 mV
, (16.116)
which has a value of 23 using the wind parameters above and I1 = 19 using the exact
solution of eq. 16.103.
The fact that lhe 1'1 has such a large value may first seem paradoxical (see Section
16.5). However, the momentum conservation in a simple mo-panicle collision does
not apply here. In the interacting winds situation, the kinetic energy of the fast wind is
first converted into internal energy of the bubble. whose then'nal pressure then drives
the expansion of the shell.

16.4.3 Transition from Ionization Bounded to Density Bounded

Assuming that the outer shock is isothermal, the density in the swept-up shell is given
by eq. 16.71. where on is the density of lhe AGE wind just outside of the shell. From
eq. 16.70, we have
434 Interaction between Star: and the Interstellar Medium

.‘ — 411111521!
1-. (a):
an ' a."17)
Since R, = V,t. the shell density falls off as ,-2._

M 1 _,_
10, =——t
47:12:15 . (16.118)

Using the same wind parameters as before and assuming a sound speed in the shell of
10 km s I and 11 = 1.4, the number density of the shell at t = 5000 yr is ~ 860 cit-r3,
if we compare the mass of the shell

M, = 4IrR,1AR,p,

M —-v, 2
= — 1/ (00) AR , (16.119)

with the expression for the shell mass in eq. 16.104. we have

AR,_ __1 fl 2
Rs -(1 Vs)(vs) . (16.120)

Since V, is a constant, the ratio of the shell thickness to shell radius stays constant
with time. With the same parameters as used previously. AR,/ R, 2 0.07. The thin
shell approximation that we have adopted before is therefore justified.
The ionization state of the shell is determined by the Lyman photon continuum
output from the central star and the recombination rate in the shell, which is given by
eq. 16.74. Substituting eqs. 16.117 and 16. I 19 into eq. 16.74, we have

. 2 2
Q: = (fl) (ELB)( l ) (v, — V)t—1. (16.121)
V 411' count...

In contrast to the interstellar bubble case, Q, does not increase but decreases with
time. This is because in the [SW case. the rate of mass sweep-up is a constant. not
increasing with time. With the shell density decreasing as t 2 and A R,/ R, = constant.
I nfid V of the shell decreases as t". Since the fluxes of the optical emission lines are
proportional to f 1-1de of the ionized region. the evolution of the ionization structure
has an important effect on the observed morphology of the nebulae.
For a, = 2.59 x 10-‘3cm‘ s". x, = 1.17, and the same wind parameters as
before, eq. 16.121 gives Q, = 2.3 x 10"6 s I att = 5000 yr. Planetary nebulae evolve
with constant luminosity across the H- R diagram. As the temperature of the central
star increases. the Lyman continuum output increases rapidly with time. When Q >-
Qc, the nebular shell will go from ionization bounded to density bounded. After the
central star reaches its maximum temperature and evolves dostrnward in luminosity.
Q drops again and eventually the shell will undergo recombination (Fig. 16.6).
 “5.4 Interacting Stellar Winds 485

5 I I fii I I

- J

a """"""""""""":
E” .'-.|I
.’ .
-.\
'\
\ _
. \ ----
.‘ t\ ........
'- \ ———- -
\
\

1 I I l I l

5.5 5.0 4.5 4.0

log TIll (K)

‘ TIIIIII'I l [VIII-III I lllll'l'l'l l IIIII'I'I'I I I'll

I03:— 1

"i: __
: I02
0 l5- :

I' _

10' "- - .
10' IO2 10J IO‘ [0’ 10°
Time(years)

Figure 16.6
Left: the evolution of planetary nebulae with five different central star masses across the H—R
diagram. Right: the changing Lyman continuum output for these five nebulae. The peak of (2
corresponds to the maximum temperature reached during the constant luminosity phase. The
subsequent decrease in Q is due to declining stellar luminosity.
486 hirer-action between Star: and the Interstellar Medium

16.5 The Momentum Paradox

High-velocity outflows from star formation regions were first discovered by the
detection of extended wings of the CO I = l — 0 line. Maps of the high-velocity
emission regions show an anisotropic angular distribution of the red-shifted and blue-
shifted components. suggesting a bipolar outflow. Centers of these outflows often
coincide with strong sources of infrared emission that represent sites of recent sun-
forrnation. Bipolar outflows have been observed in both high-mass (e.g.. Orion) and
low-mass (e.g., T Tauri stars) star formation sites. and may con-espond to a univerm
evolutionary stage between the collapse of the parent molecular cloud and the eventual
formation of new stars.
The amount of mass contained in the outflow can be estimated from the antenna
temperature of the molecular line (Section 9.3). and the velocity of the flow can be
measured from the extent of the line wings. The derived momentum of the outflows is
found to greatly exceed the photon momentum of the central source (M V >) L./c),
and this has led to the suggestion that such outflows cannot be driven by radiation
pressure of the central star.
Since these high-velocity outflows are often embedded in molecular clouds. it is
possible that the observed mass in the flow is due to swept-up. rather than ejected.
material. Although the observed flow velocities are high compared to the local sound
speed, they are low compared to the escape velocity of the central star. This suggests
that the flow has been significantly decelerated since its ejection from the star. The
fact that larger flow sources seem to have lower velocities also points to deceleration.
It should also be noted that while the observed flow momentum seems to exceed the
photon momentum. the mechanical luminosity (finial) of the flows is only a small
fraction of the luminosity of the central srar.
it is therefore likely that the observed high-velocity flows are the result of
interaction of an observed stellar wind with the circumstellar molecular cloud. in such
case. the flow is not necessarily momentum conserving and it would be inapprOpriate
to compare the momentum of the flow to that of the radiation field.
Let us assume that the high-velocity flow is centered on a star of luminosity
L... embedded in a molecular cloud with a density distribution of the form p(r) =
po(r/ro)5. A stellar wind is then ejected from the star at time t = 0 with a steady
mass loss rate rim and velocity v. Assuming the radiative loss to be negligible, the
dynamics of the flow is governed by eqs. 16.93. 16.96, and 16.97.
Assuming that the ambient mass is at rest (V = 0), the solution to these equations
can be found by similarity analysis as in Section 16.3. The radius (R,). velocity
(V, = dR,/dr), and mass (M,) of the swept-up shell are

]U(fl-t5] {16122)
R,(r) = |:Crirul(f.lorc;fl)_ItJ

11,0) = 3—59 (l6.l23)

.5 + 5 r
 16.5 The Momentum Paradox 437

M,(:) __ e—+
4" 3 [Cmu
- 2 (WtJ—1B ) 2/(e+3) :]
:1 (“”5””) (16.124)
3‘2"} +7)
P =— - 2 —fi memo—411mm WWW” .
0) (“one”)? x[ C "w W“ ) r
]
(16.125)
where C = (,6 + 3)(,B + 5)3/ [123(219 + 7)(fl +11)] and 15 5e —3, —4. -5. —7/2.
or —1 1.
Substituting the preceding solutions to eq. 16.112. we see that the energy effi-
ciencies of the flow are independent of time:

3(fl + 5)
= ___ (16.126)
(2)9 + mp +11)
Table 16.1 lists the values ofe for several values of 15. and we can see that the efficiency
of convening wind energy to shell energy increases with increasing density gradient
in the ambient gas. The momentum efficiency 11. however. is generally a function of
t. From eq. 16.115. we have

[2.7! _. ”0+”
11 = __ cfi+4 ' —1 fi+3 19 3+1 ’ 16.127
(19 + 3103 + 5) l m ” (M )' l ( )
which is a constant only in the case of ,8 = —2. Expressed in astronomical units.

_
"=4L3l:[nfll(r—lpc)/I03cm -3 ](u/1000krns —1 )] ”3 (16.128)
(151/10-6 Me yr")

for ,6 = —2. We can see that in an energy-conserving flow. the momentum of the
swept-up material can be many times the wind momentum. To decide whether radia-
tion pressure is the respousible mechanism for the outflow. one has to compare m to
L./c, but not M, V,
In this model. there are four parameters (,6, Lu, = 112111111. p0. and t) to fit three
observed parameters My V3, and 11,. However. there are physical constraints on these
parameters and they are not entirely free. In a radiatively driven wind. 11 is expected to
be several times the escape velocity. Self-similar solutions to the gravitational collapse
of molecular clouds show that )6 = —3/2 in the inner regions and fl ~ -2 for the outer
regions. Values of pa are also restricted by line observations of the molecular cloud.
Usingtheideal gas law and eqs. 16.107 and 16.125, we can obtainthetemperature
of the shocked gas:

r 2
1“,: (fl) “mt!” . (16.129)
15 +11 1':
488 Interaction between Sm rs and the Interstellar Medium

Table 16.1
Efiicicncy in converting
wind to shell energy

fl e

0 0.l9
-l 0.24
- 1.5 0.28
#2 0.33

We can see that the efficiency of converting kinetic energy into heat decreases with
increasing Ifl I. This is because a larger fraction of energy goes into the expansion of
the shell at higher |fl| (see Table 16.1).

16.6 Summary

The discoveries of high-velocity stellar winds from OH stars and central stars of
planetary nebulae and their subsequent interactions with interstellar and previously
ejected circumstellar materials have fundamentally altered our understanding of H II
regions and planetary nebulae. High dynamic-range narrow-band optical imaging of
planetary nebulae have revealed multiple-shell structures (shells. crowns. haloes) that
are well explained by detailed hydrodynamical models coupled with photoionization
calculations bascd on stellar evolutionary tracks. Diffuse X-ray emission predicted
to have arisen from the “bubble” have now been imaged by the Chandra X—Ray
Observatory Advanced CCD Imaging Spectrometer.
The dynamical output of stars is now recognized as an important agent of in—
teraction with the ISM. in addition to their radiative inputs. The hot (Th ~ [0'6 K)
component of the ISM. recognized through their X-ray continuum and [0 IV] line
emissions, is the result of wind and supernova interactions with the general ISM.

Further Reading
Dyson. J. E.. and Williams. D. A. 1997. Physics ofthe Interstellar Medium. IOP. provides
an elegant mathematical treatment of shocks and their interaction with the 18M.

Exercises

1. In an adiabatic monoatomic ideal gas. the maximum amount of density compression

possible by a shock wave is a factor of 4. Calculate the Mach number ofthe post-shock
gas (MI = til/a.) for a strong shock (MD -> oo).
 Exercises 489

2. A supernova instantaneously released 105l erg of energy into the ISM made up of pure
H at a density of l cm‘3. Assuming that the shock wave generated by the explosion
expands adiabatically into the interstellar gas.

- calculate the velocity and radius of the shock from after 10,000 yr.
0 calculate the temperature and density of the gas immediately behind the shock
front.
' estimate the thickness of the swept-up gas and rate of energy loss due to f—f
emission at this time.
 17
Beyond the Galaxy

17.1 OVeraIl Structure of the ISM

In the past 30 years, we have learned through the observations in the radio. millimeter,
infrared. optical. ultraviolet. and X-ray spectral bands that the ISM is far from being
homogeneous. Interstellar matter exists in densities ranging from 10‘2 to 10‘5 cm‘a.
and in temperatures from 10 to 107 K. Since stars represent the major source of energy
in the Galarty, the rich state of the ISM can be traced to the radiative and dynamical
interactions between stars and interstellar matter. Since nucleosynthesis only occurs
inside stars, stars are the only source of processed matter. and stellar evolution is the
driver of chemical evolution of the Galaxy.
In the previous chapters. we have described a variety of physical and chemical
processes that are active in Ihe ISM. Most of the energy transfer between stars and
interstellar matter occurs radiatively. Interstellar gas. in particular, H, intercepts ultra-
violet light from hot stars through photoionization (Section 4.3). The ejected electrons
then heat up the surrounding gas through collisions (Section 6.5). Recombination of
the free electrons with H (Section 5.! I) or heavy element ions (Section 5.14) resqu
in electrons in high electronic states, which then Cascade to lower states by emitting a
series of recombination lines. The free electrons can also collide with atoms and ions
and excite them to low electronic states within a few eV of the ground state. Even if
these states are melasrable. they can still have time to decay due to the low density
of the ISM. These collisionally excited forbidden lines. both in the visible and in the
infrared. represent a major source of cooling of the ISM (Section 5.12). The net re-
Sult is the conversion of the high-energy stellar continuum photons to low-energy line
photons that escape from the Galaxy.
In other regions of the ISM away from hot stars. the transfer of energy from stars
to the [SM is through visible light. Most slats radiate primarily in the visible, and
these photons are easily intercepted by interstellar dust. Dust grains heated by stellar
radiation can cool themselves through the releaSe of electrons via the photoelectric
effect (Section 10.9), which is the primary source of heating of gas in the neutral
atomic component of the ISM. These radiatively heated grains can also transfer energy
to the molecular gas component through grain-gas collisions. a process that can be
important in PDRs.
492 Beyond the Galaxy

The thermal energy of dust grains that is not transferred to the gas can be lost
through self-radiation, which occurs primarily in the infrared and the subnun Wave.
bands (Section 10.3). The emitted dust radiation can be absorbed by the molecular
component of the ISM. exciting the molecules to vibrational states. The lower to-
tational states of molecules can be excited by collisions. The subsequent decays of
molecules from their excited vibrational and rotational states lead to infrared. subn-n-n,
and mm line radiations. The escape of these photons from the clouds allows the clouds
to cool. When the cloud temperature is low enough to satisfy the Jeans criterion (Sec-
tion 15.5), gravitational collapse commences. leading to the formation of new stars.
In addition to radiation. stars also inject mechanical energy into the ISM. Massive
stars have strong Stellar winds throughout their lifetime (Section 15.6). and these
winds create interstellar bubbles of high temperatures (Section 16.3). At the end
of their lives. massive stars undergo supernova explosions (Section I62). which
transform stellar gravitational energy into mechanical and radiative energy. The strong
shocks generated by supemova explosions are major agents for the creation of a hot
ionized medium in the ISM.
For low- and intermediate—mass stars, which encompass 95% of all stars in
the Galaxy. their interactions with the ISM are less in terms of energy input. but
more in returning mass and processed materials to the ISM. Stellar winds from
AGB stars represent the major source of mass replenishment of the ISM. and AGB
nucleosynthesis and grain formation play major roles in the chemical enrichment of
the Galaxy. The connection between these AGB ejecta to the primordial chemical
makeup of the solar nebula is not yet well established. but nevertheless represents a
promising area of future study.
Stars are factories that convert nuclear energy into visible and ultraviolet light
This radiative energy is then converted by interstellar dust and gas into lower-energy
visible. infrared, mmlsubmm. and radio line and continuum photons. This is analo-
gous to a biological food chain that begins with the conversion of sunlight to chemical
energy by plants. which are then cousumed as food by animals and spent in the form of
kinetic energy through motions. The interaction between radiation and various forms
of matter therefore leads to the rich field of astronomy that we have today.

17.2 Radiative Interactions between Different States of Matter

We now know that there are celestial objects (e.g.. planetary nebulae and active galac-
tic nuclei) that are active throughOut the electromagnetic specuum from radio to
X-ray. Such rich emission specna reflect the presence of different states of matter.
Strong emission lines in the visible and UV arise from ionized gas, and the large
infrared excesses observed are due to dust emission. Molecular emissions due to to-
tation transitions suggest the presence of neutral matter. Planetary nebulae and active
galactic nuclei contain a central heating source (a hot star and accretion disk. respec-
tively) that is responsible for the photoionization of the gas. The nebular enrission
then heats the dust. whose infrared emission in turn excites the molecular gas. The
intrigue coupling between the different components requires a more comprehensive
treatment of the radiation transfer problem.
 17.2 Radiative Interactions between Drferen! States ofMarrer 493

Photodissociation
model

Dust continuum Molecular-line

Central energy Photoionizau'on . . . .
souror. model radrauon radratron
transfer transfer

V ‘F V

Visible 0P”“’_ UV and optical Infrared ”‘3‘”

continuum and radio emission fines continuum 5 'mrrt
continua emtssran tines

Figure 17.!
A flowchart illustrating the numerical procedure on how the interactions between the central heating
source. the ionized gas. neutral gas. and dust components can be solved.

A complete self-consistent model taking into account the radiative interactions of

the ionized. dust. and neuu-al gas components can be made using different numerical
codes for photoiouization. pholodissociation. dust continuum transfer. and molecular-
line transfer. First. the ionized gas component is treated independently. The ultraviolet
output of the central energy sources is fed into the photoionization (Section 4.6) and
photodissoeiation (Section 14.2) models to determine the extents of the photoion-
ized and PDR regions. All the permitted lines with significant optical depths (e.g..
the recombination lines of H and He) have their line transfer problem solved with
the escape probability method. The output of the photoionimtion model, including
the fluxes of the recombination lines of H and He. the collisionally excited lines of
metals. b-f and f-f continua. and the stellar continuum. is fed to the dust continuum
transfer problem as the input radiation field. The dust continuum transfer equations
are then solved. producing continuum averaged intensities (1..) at every radius. If the
molecular gas is well mixed with the dust cornponent. the values of J..(r) are used as a
source of background radiation available for the radiative excitation of the molecules
(Section 9.6). The equation of transfer and the equation of statistical equilibrium are
then solved for the relevant molecules (e.g.. C0) to produce the emergent fluxes in
each of the rotational transitions (Section 9.7). A flowchart illustrating this process is
shown in Figure 17.1.
An example of such a model spectrum is shown in Figure 17.2 for NGC 7027
over the wavelength range 11000 A to 1 cm. Most of the lines in Figure 17.2 in the UV.
494 Boond the Galaxy

9.
Model it: (Wm 1)
Ei
5L
3.
'5.

I 11111L11\1 titJmJ _l llllllll J_llllllJi L4

10" [0° 10' 10‘l 10’
Wavelength (pm)

Figure 17.2
The model spectrum of NGC 1027 from W to radio. The thin (almost straight) line on the left
is the continuum spectrum of the central star (usumed to be a 226.000-K blackbody). which
is the sole source of energy. The conversion from a simple photospheric emission of a single
star into a complex of emissions via many mechanisms is a manifestation of the radiative
interactions between different states of matter (from Vollr and Kwok 1997. 41171.4”. 722).

visible. and infrared are recombination lines of H and He and collisionally excited
lines of metals. In the submillimeter region. the rotational lines of CO and H20 are
plotted. In the mid and for infrared. the continuum emission is dominated by the
dust component. The major AIB features at 3.3, 7.7. 3.6. and 11.3 um can be seen as
narrow features. At wavelengths longer than A400 pm. thef-f continuum begins to be
stronger than the dust continuum. The visible and near-infrared continua are marked
by the H and He 19-)“ jumps. The broad feature near 2400 A is the 2y continuum. The
absorption feature seen in the near UV is the 2200-}! feature. The blackbody spectrum
of the central star is plotted as a dotted line.

17.3 Application to Extragalactic Astronomy

Many of the concepts covered in this book can find direct applications in extragalactic
astronomy. The photoionization sanctum discussed in Chapter 4 can be applied to
active galactic nuclei. where an accretion disk replaces the central star as the energy
source. The spectra of quasars and active galactic nuclei (Fig. 17.3) are dominated
 17.3 Application to Extragalactic Astronomy 495

' t I . rrrm I

F05 quasar spectrum

10 .— Lye. + N v _

B - -
. E .

,. 6 '
a“
21 3I ‘
r 4
I:
3 3 a
0
E
"
-
o J’ + <
.g e i ‘

n‘ 2

l
0.8
. ....... . . . . "ml A

400 600 800 1000 2000 3000

Rest-frame wavelength (A)

figure [1.3
Composite HST Faint Object Spectrograph spectra of IO! quasars showing several prominent
emission lines in the ultraviolet (from Zheng et al. 1997, ApJ', 475. 469).

by permitted and forbidden emission lines, including many of the ultraviolet lines
discussed in Chapter 5 redshified to tlte visible.
In the early Universe where the metal content is low. cooling by heavy elements
is much reduced and the gas temperature of any photoionized regions will be high
(Section 6.5). Since the H recombination rate decreases with increasing electron
temperature (eq. 4.42). a lower recombination rate means that the extent of the H II
regions will be larger. Given the presence of very massive stars in the first generation
of star formation, the Lyman continuum output will be very high, leading to a further
increase ill the extent of the H II regions. Without heavy elements to form grains.
molecular hydrogen cannot form on grain surfaces (Section I43). With a limited
abundance of H2. there would be very little in the way of shielding of UV photons
longward of the Lyman limit and the diffuse interstellar radiation field (Section 4.7)
will be very different.
The absorption coefficient of the Lyman at line discussed in Section 5.1 l forms
the basis of the Gum-Peterson effect. Continuum photons longward of the Lyman
a line emitted by distant quasars can be scattered by intergalactic neutral H between
the quasar and the observer. Because of the high absorption coefficient of the Lyman
at line. successive layers of intergalactic H can effectively remove the continuum of
distant quasars. The measurement of the continuum blueward of the Lyman at line
in quasar spectra can therefore be used to infer the density of intergalactic H. The
496 Beyond the Galaxy

detection of such a continuum would imply that the density of intergalactic H is very
low, or H is in an ionized, not neutral state.
111ef-f emission formulae in Section 6.3 can be used to interpret K-ray ammo“
from galaxy clusters to derive mass and temperature distributions of the hot gas By
combining the equation of hydrostatic equilibrium (eq. [5.27) with the equati0n of
state ofan ideal gas (eq. 16.16). one can derive the mass distribution in galaxy clusters;

k dT dp
M = —— -— T— .
(r) um" (p dr + dr) (”'1)

This is a common method for determining the mass-to-light ratio of galaxy clusters
and therefore the distribution of dark matter.
A possible major source of unseen baryon mass is molecular hydrogen. As
discussed in Section 7.7.1. H2 is diflicult to detect and its abundance in the Universe is
uncertain. Most of our estimates of the molecular gas mass are based on extrapolation
from the abundance of C0. which can be easily excited and observed. Even when
the 23-pm Hz rotation line is observed. it traces only the distribution of warm H2
at temperatures of a few hundred degrees. For H; in the Milky Way Galaxy, its
presence can be detected through vibrational-rotational transitions in the Lyman
band through UV absorption spectroscopy (Fig. 7.13). at least along lines of sight
where a background UV continuum source is available. For molecular hydrogen in
distant galaxies. it can be detected through their vibrational—romtional transitions
by infrared spectroscopy if there is a strong infrared background continuum source.
Given adequate spectral resolutiou. the equivalent of the Lyman a forest in H; can
be seen.
In the early Universe. the light elements H. He. D. Li. and so on are produced
by primordial nucleosynthesis. At redshifts of z = 200—400, the temperature of the
Universe is low enough that photodissociation can no longer prevent the formation
of molecules. The most likely candidates for primordial molecules are H1. H2". HD.
HD‘. HeH+. Lil-l. and Lil-1+. Since there are no grain surfaces for H2 formation.
molecular hydrogen is likely to have formed through gas—phase reactions. for example.

H+e—>H_+hv
H‘ +H—> H2+e (17.2)
H+H+—>H;'+hv
H; +H—>H2+H+ (17.3)
In order for the first stars to form. the gas first has to cool. otherwise the Jcans mass
(eq. [5.82) would be too high. Molecular hydrogen and HD are the most likely agents
for cooling. Primordial molecules therefore play an important role and represent a new
area for future study.
Given a lack of alternative excitation sources such as collisions and other back-
ground radiation. primordial molecules are excited only by the cosmic background
 f 7.3 Application to Extragalactic Astronomy 497

radiation. and are therefore radiatively coupled to it. Consequently. there are no ob-
servable emission and absorption processes if the molecules are in thermodynamic
equilibrium with the cosmic background. However. if the molecular source has a
particular velocity along the line of sight, resonance scattering of the rotational tran-
sitions can produce secondary anisotropy in the cosmic background radiation. just
as electrons do through Thomson scattering. Although the abundance of primordial
molecules is low, the cross Section of the resonance of molecular rotational transitions
(eq. 9. l 5) is many orders of magnitude larger than the Thomson scattering cross sec-
tion (eq. 5.52). This process could be important in the era before reionization. where
electron scattering through the Sunyaev—Zel'dovich effect becomes dominant in the
creation of secondary anisotropies in the cosmic background radiation. Being a line
process. scattering by molecules can be distinguished from the Sunyaev-Zel'dovich
effect by its strong frequency dependence. The profiles of primordial molecular lines
can therefore be used to infer the kinematics of large-scale structures when the Univ
verse was cold.
An increasing number of molecular lines have been observed in galaxies. The
rotational transitions of C0 have been seen in quasars with high redshifts (z > 6.
Fig. 17.4}. suggesting that stellar nucleosynthesis and molecular formation have taken
place before the Universe was 109 yr old. Assuming a certain COIHZ ratio (Section
9.4), one can derive from the strength of the C0 line a total molecular content of
.> 10“) M:,. which can be used to infer star formation rates > 103 M5. yr" in the
Galaxy.
The cool. diffuse component of the ISM in galaxies can be traced with the fine-
su'ucture lines of C t (Section 5.3). Figure 17.5 shows the broad C 1 emission from
the ultraluminous infrared galaxies Arp 220 and NGC 6240. With future powerful
submm instruments such as ALMA. the C t line can be routinely detected and mapped
in distant galaxies.
Observations of galaxies have the advantage that the spectrum reflects the entire
energetics of the [SM in the galaxies. Starburst galaxies (e.g.. M82 and Arp 299) show
strong fine—structure lines such as [C II] (Fig. 17.6). whereas the infrared spectrum of
the ultraluminous galaxy Arp 220 is dominated by absorption lines of 0H (Table 7.9).
H10 (Table 7.6). CH, and [0 t] with only weak [C It] emission. These observations
allow one to characterize stellar populations and their effects on the ISM.
Since most of the molecular gas is in the form of Hz. the best way to directly
estimate the total mass of the molecular component is to observe the ground—state
quadrupole rotational transitions of H2. provided that the gas is warm enough to
excite these levels (Section 7.7.1). Figure 17.? shows the observation of the three
lowest rotational transitions of H2 in NGC 3556 by the Spitzer Space Telescope.
Infrared luminous galaxies (lRLGs) refer to the class of galaxies that have strong
dust emission in the far-infrared and submillimeter wavelengths. lRLGs typically
emit > 1045 erg s ' through dust emission. which can exceed their output in visible
starlight. IRLGs generally belong to either active galactic noelei (AGN). or starburst
galaxies. which are infrared luminous galaxies undergoing active star formation.
The strong dust emission in starburst galaxies is believed to be powered by newly
498 Beyond the Golan

Redshift
4.1 4.11 4.12 4.13 4.14
15_"Ifi—'"I"'rl""I""II‘
' COM—)3] I
g. to - Zoe 1
E :
3‘ 5 r ‘.
3 : [1'1
K
E 0.11 ililiiltrl— r}“¥1 T+ 1
: T W 1
—5:l . i_._. . l _t_ . L . . I ._
411K) 0 1000
Velocity ofl'set(kms I)

Redshift
4.1 4.11 4.12 4.13 4.14
15 _. .—l . I . . 1—- . . . ' .—. r . I . . . . 1—.

E
3:10 ~ Zap
s E
b —

up. 5 p .

gE E.
E 0_ F

_5:r . J . . . . I . . . . 1 _.
—1000 0 1000
Velocity ofl'set (km s ‘)

Figure 11.4
The redshifted CO rotational transitions from the quasar PSS 2322+1944 (z = 4.12). The
integrated line strengths of the C0 lines suggest a total molecular mass of 2.5 x 10“ M3.
From nun continuum data. the dust mass is estimated to be L6 in It)9 Mm (from Co: at at.
2002. AM, 387. 406).

formed massive stars. Molecular emission from the collapsing molecular clouds and
the photoionized regions is manifested in the rich emission-line spectrum in the optical
and molecular emission in the rru'nlsubmm regions. Figure 17.3 shows the infrared
spectrum of the starburst galaxy M82. The spectrum is dominated by strong dust
 [7.3 Application to Ertragalacu'c Artronomy 499

T.' (K)

_._ I _I_ .

5000 5200 5400 5600 5800

Velocity (Innis) LSR frame

4‘1 4“

‘F000 1500 8000

Velocity (ltmls) 15R frame

Figure 17.5
The redshified 492~GHz fine-structure line of C I (shown as thick lines) in Arp 220 (top) and
NGC 6240 (bottom) observed at J'CMT. The spectra of ”co (1 = 2 - I) and 10x l3c0
(J = 2 — 1) (shown as the upper and lower thin lines. raspectively) are also plotted for
comparison (from Papadopoulos and Crew 2004. ApJ'. 615. L29).

continuum emission. peaking at ~ 60 um. corresponding to a dust temperature of

~ 50 K. Many of the strong emission lines (Ne n, S In, Si ll. etc.. Table 5.7) arise
from the photoionized region. but some of the fine-structure lines (e.g.. 0 I. C n) arise
from the PDR (Socu'ou 14.7). M32 also shows strong AIB emission features at 3.3.
6.2. 7.7. 8.6. and [1.3 pm (Section 12.1). The depression around [0 pm is not due to
absorption by amorphous silicates, but is the result of strong emission plateaus around
8 and 12 um (Section 12.7).
5'00 Beyond the Galaxy

[fir‘rI—I Irrlfi I Fl l‘r‘l I I . .

I‘l—III'

]_l_ll_l_l
0H

l
l—I'l—H— I l

_l_l

“I:
O

J
=I

—
Ill I'lll'

Illllll
CH
|

I
_|_

E- Arp 220
E.
- NGC 4945 3

“a: :— 1
'2 NGC 253 S

L Can A _

i 1

l- M 82 .1

:_. >l >

l I >I >l I >l Arp 299 _E
E x 3 > :2: " > 0 j
- n m o n In 0 --
— II H i II T; fi I 1
' “fit-.1“ ".1.“ “4° I-uEl “In '
I- E E '= E 'E 7: '3 fl
2 E 2. 2. E. 9. H
I J— I I I I L I I I I I— I I I I l_l I I

50 100 150 200

Rest wavelength (pm)

Figure 17.6
(50 LWS Spectra of six infrared bright galaxies. All spectra have been shifted in wavelength
to Its! wavelengths (from Fischer et al. [999. Ap. Sp. Sc. 266. 9]).
 I 7.3 Application to Extragalactic Astronomy 501

NGC 3556
4

E 2_

3 :— —Z

s E i
g 2 2— —:
E 3

0 ' Z

10
Wavelength (pm)
1110—0 5(2) H2 0-0 5(1) H20—0 5(0)
Lo ' I . I 'l" I 1.0 "l "l""_l_' ' 2.0 1' "1' I

0.8 0.8 ‘1’ 1 1.8 J,

3 0.6 - 0.6 1.6

E"- 0.4 0.4 - 1.4 PF

0.2 0.2 1.2 -

0.0 . l l....| ..I 0.0 .I... I . I Lottidnnlnnh...

”.0 [1.5120 12.5 I10 16.0 16.5 17.0 17.5 18.0 21.0 27.5 28.0 28.5 29.0
Wavelength ( pm)

Figure 17.7
Spitzer Space TelesL-Ope Infrared Spectrograph (IRS) high-resolution spectrum of Ihe nearby statburst
galaxy NGC 3556. 111a three marked lines (from left to right and expanded in the louver panel) are
the H2 0 = 0 - 0. 5(2) (12.23 urn). S(l) (17.03 pm). and 3(0) (28.22 um) lines. respectively. The
broad feature left of the 5(2) line is the 11.3-prn AIB feature (courtesy of the Spitzer—IRS team at
Comell University and D. Deva and J. Bernard-Salas).
502 Beyond the Galaxy

1000
[N6 Ill [Si III 200 77

$3.
[S III] - 62

100 " 8.6

"a,
N
§
600 _
EU _ [S In]
E“
§ § § §
0
E'.
'2
E
*1

o 20 4o 60 so 100 [20140160180 260

Wavelength (pm)

Figure 11.8
The ISO SWS and LWS spectrum of M82. M82 is the brightest galaxy in the infrared and is
considered as a prototype of starburst galaxies. At a distance of 3.63 Mpc. the total infralul
luminosity is 3.8): l0l0 10- In addition to strong dust continuum and fine-structure forbitkkn
lines. the spectrum also shows very strong AIB fearttres (insert).

In addition to the family of aromatic emission features. the aliphatic feature at

3.4 pm (Section 12.l.l) can also be seen in the spectra of lRLGs (Fig. 17.9). This
suggests that the synthesis of complex organic compounds is actively ongoing in
lRLGs.
Many lRLGs show the 10- and lB-um silicate feature (Section 11.2.1) in ab-
sorption. suggesting that silicates are a common dusl component in these galaxies. If
quasars are the pole-on counterpans of these galaxies. then the silicate features should
be seen in emission. Observations by the Spitzer Space Telescope Infrared Spectro-
graph have found that this is indeed the case. Several infrared spectra of quasars
showing the ID- and IB-mn feature in emission are shown in Figure 17.10.
A survey of the cosmic far-infrared background due to dust emission from distant
galaxies can be used to trace the peak of star formation and metal production historiel
of galaxies. Using a standard SED of star-forming galaxies and taking into account
the gradual redshift of the AIB features to longer wavelengths. one can determine
the epoch of dust formation from source counts in far-infrared surveys. For example.
sources in the 24-,urn band of the Multi—Band Imaging Photometer (MIPS) of the
Spirzer Telescope could be dominated by ME emissions from galaxies at 2 ~ 2.
 17.3 Application to Enragalacn'r: Astmnomy 503

_ ' I ' I ' 1 ‘

20 - [€694 -

A I i I
"515 f .4 -

IE _ 3‘
23 IO _- + J. Pfif ‘
b - t o I '
E" i d i, ¢ 1
5 _ ”cw’ W14” wmflhwh§W+a++w fi-fi

rF i
0 b a. l a I I ‘

3.2 3.4 3.6 3.3

Wavelength (,um)

20 ' _l_ '— —l_ r —r

NGC 6240

7“ 15' l. —
“5. f 0'

fE 10C. ai ,a i 1120—0305) i
'9 : i 0c h I 2
a; 5 9+”? was". ““fi‘sfia’mmflnn‘r‘ae ”my;

L I
o l 4L | 4. l

3.4 3.6 3.8

Wavelength (,um)

Figure 17.9
The UKIRT cooled grating specn'ometer spectra of [111.03 1C 694 (z = 0.010) and NGC 6240
(1 = 0.024) showing the 3.4-um aliphatic emission Tenant. The positions of the redshifted
3.3-,um aromatic and the 3.4-um aliphatic features are marked by arrows (from lrnanishi and
Dudley 2W. ApJ. 545, 701).

Even unidentified emission featms such as the ERE (Section 12.4) are seen in
external galaxies. Figure 17.1] shows the spectrum of ERE emission in lhe halo of
M32.
The submillimeter excess as found. for example, by the SCUBA bolometer array
on the JCMT is indicative of cold dust (Fig. 17.12). The dust mass in these galaxies is
often obtained using optically thin. unifon’n-temperatm'e models (eq. [0.23) assuming
a certain dust emissivity pam-neter (a. eq. 10.15). As the quality of observations
504 Beyond the Galaxy

[.0

0.3

9
ch
flux density [Jy]
.0
es

0.2

- Q; P00304-
0'0 l I H'- i ‘ l J I: i j i 1 7 I I

7 B 9 ID l2 15 20 30 40
Rest wavelength (11ml

Figure 17.10
Continuum-subtracted IRS spectra of five quasars showing the It]- and IS-um silicate feature
in emission (from Hao er al. 2005, ApJ. 62.5, L75).

improves in the future. the fitting of the dust spectrum of galaxies can be fitted by
radiation transfer models. as is now commonly done for galactic dust clouds.
The existence of Extremely Red Objects (R — K > 5) and SCUBA sources with
faint or no optical counterparts suggests that there is a population of high redshift
galaxies whose energy output is dominated by dust emission. While it is clear that dust
is present in the early history of the Universe. it is not known whether the intergalactic
medium contains a significant amount of dust. This question may have implications
on cosmological models because extinction by a population of grey dust can mimic
cosmic acceleration. therefore bringing into question the need for "dark energy."
The evolution of both high- and intermediate-mass stars is heavily dependent on
the mass loss rate. Given that radiation pressure plays a key role in the mass loss
process. the dependence of mass loss rate on metallicity is therefore an important
problem. The first-generation stars would have no heavy elements and therefore no
resonance lines to drive the mass loss. resulting in a higher core burning rate and
accelerated evolution. Intermediate-mass stars, without grains to serve as a source of
 I73 Application to Euragaiactic Astronomy 505

34000.0 6000.0 3000.0 4000.0 6000.0 3000.0

WaVelength (A) Wavelength (A)

Figure 17.1]
Left: An excess of red continuum emission can cleafly be seen in the halo of M82 after dividing
the observed spectrum by that of the galaxy. The profile of the ERE emission after subtraction of a
scattering continuum is shown on the right (from Pen-in er al. 1995.14.91. 30‘. L21).

10 ' ' 100 1000

3.01m)

Figure 17.12
The spectral energy distribution of the dwarf galaxy NGC 1569 fitted by a multicomponent dust
model (from Galliano er a}. 2003. AM. 407. 159).
506 Beyond the Galaxy

opacity. cannot lose a significant amount of mass on the ACE and most of them
will become supernovae. Stellar evolution and the initial—final mass relationship
will be very different at different metallicities. and will be a function of galactic
chemical evolution. The population synthesis method used to model the spectra]
energy distribution of galaxies therefore cannot rely on the evolutionary tracks of
the current generation of galactic stars, but will have to include the effects of the
different modes of stellar evolution at different redshifts.
Although explosive events were fashionable in the 1970s. we now recognize that
winds or steady outflows are more comtnon and interactions between different mass
outflow episodes can have interesting consequences. The interacung winds process
discussed in Chapter 16 has found many applications in extragalactic astronomy,
including gamma-ray bursts, relativistic jets in active galactic nuclei, and galactic
superbubbles. Although we have restricted ourselves to one-dimensional models. the
extension of the models to 2-Dcan account for many of the basic structures in a unified
AGN-quasars-BL Lac model.
P Cygni profiles resulting from fast stellar winds of massive hot stars can be seen
in the spectra of galaxies even at high redshifts (Fig. 17.13). These spectroscopic

1 ‘|'—_l_ —l——l —l_ r—I' I—l I I l

5 N5 0347—333 2 = 3.239
T—F‘T—r—T
f, (My)
N

.................. .t. .u-.\ l

F‘T—r—_T-_l'——'I'T

NGC4214;
I . i
. l E
: E 5 en : a" : o
0 ......................... g i ..... §§ E... "'3 fi'fi .............. ENE ...............
E a Z : Z 2 E z = a
a it it? o o a a u :2 4:
l l I I I I I J I J l I l I I

5000 6000 7000

Wavelength (A)
Figure 17.13
Signatures of stellar winds from massive 0 stars can be seen in the spectrum of a z > 3 galaxy (top)
and a nearby starburst galaxy NGC 4214 (bottom). The spectrum of NGC 4214 has been redshifted
to coincide with that of the high-z galaxy. P Cygni lines of C iv and Si N (tedshifted to the visible)
can clearly be seen (from Steidel er al. 1996. Astrophys. J.. 462. L17).
 17.3 Application to Extragalactic Astronomy 50?

signatures suggest that large-scale star formation is well under way at the early epoch
of z > 3. The injection of heavy elements. mechanical momentum. and energy by
these stellar winds into the ISM represents a srrong driving force of the chemical
and dynamical evolution of galaxies. The superbubbles created by stellar winds from
clusters of OB stars could be responsible for galactic energetic outflows observed in
starburst galaxies

One of the lessons of twentieth-century astronomy is that while the fundamen-

tal laws of physics and chemistry are no different in space than in the laboratory,
the enivronment in which physical and chemical processes occur in the ISM. the
intergalactic medium. and the early Universe is very different. A good quantitative
understanding of these processes in the ISM is therefore essential for realizing the
limitations of applying various observational techniques to exttagalactic problems.
and therefore appreciating the range of inherent errom of the derived parameters.
In this book. we do not discuss possibilities of new physics (e.g.. exotic elemen-
tary particles as the carriers of dark matter or cosmic strings as building blocks of
the Universe). but emphasize the richness of conventional physics and chemistry. Be-
fore we reach out to appeal to new ideas. it is necessary that we have mastered and
exhatIsted the possibilities of known physical priniciples. With the arrival of SO-m
class optical and infrared telescopes and sensititive radio arrays such asALMA. it will
be possible to perform spectroscopic studies of early galaxies. tight to the moment
of the first epoch of star fonnatiOn. As new observations allow us to push back into
the beginnings of cosmic time. it would be interesting to test to what extent conven-
tional physics still applies. and how its manifestations are different under different
environments.
APPENDIX 1

Vector Formulae in Diflerent

Coordinate Systems
 a . L. as ~ A L .__| an L n I w Hm hhl
mlfiulr+$mm£nvm4r+flumu¢lm+lsnb "n+mfl+flumgv%mlanb “9+ ~m+ "glans, fining...
Ea): .E .2 .< .3: € .< A: .1
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a m m I m m l n a n l
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w fit fin i o .4 a a _
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$P7+Hmm +§1<p 3+¢T+A€ta<> am+aw+am1<> 35925
smpfifl+e$m+hmmufib umm+as¢+hwmfleb uwm+qmm+_mmflob .5620
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AllM—2.

Ionization Potentials for Atoms

and Molecules

Table All
Ground levels and ionization energies for neutral atoms

Z Element Ground level [PI (eV) 11’ [I (IN) IP Ill (:V)

1 1-1 is”: 13.59343

2 He '50 24.53739 54.41776
3 Li 25” 5.39172 75.6400 122.4542
4 13: 'so 932270 13.21 115 153.3954
5 B IP11: 3.29302 25.1543 93.9306
6 c 3P0 11.2603 24.3333 47.3373
7 N ‘532 14.53413 29.6013 47.4492
3 o 3P; 13.61305 35.12113 54.9355
9 F 179512 17.42232 34.9703 62.7033
10 Ne '50 21.56454 40.96296 63.4227
11 Na 2s1 2 5.13903 47.2364 71.6200
12 Mg '30 7.64623 15.03527 30.1437
13 131 2P? 2 5.93577 13.32355 23.44764
14 51 3P0 3.15163 16.34534 33.49300
15 P ‘53,: 10.43669 19.76946 30.20263
16 s 3?, 10.36001 23.33733 34.79
17 c1 11D; 2 12.96763 23.3136 39.61
13 Ar 'so 15.75961 27.62966 40.735
19 K 1s” 4.34066 31.63 45.3060
20 Ca '30 6.11316 11.37172 50.9131

511
512 laniznlion Potentialsfor Alarm and Molecules

Table 42.1
(cominued)

Z Eltment Gmund level IP I (3V) [P H (0V) I? ll'[ (eV)

21 Sc 203,2 6.56149 12.79977 24.75635

22 T1 3F2 6.32312 13.576 27.4917
23 v Fm 6.74619 14.613 29.311
24 c: ’53 6.76651 16.4357 30.959
25 Mn 5.95,2 7.43402 15.6400 33.663
26 Fe 517.I 7.9024 16.133 30.651
27 Co 413,,2 7.33101 17.034 33.50
23 Ni 3F. 7.6393 13.16334 35.137
29 Cu 251,2 7.72637 20.29239 36.341
30 211 '50 9.39420 17.9644 39.7233
31 Ga 11". ,2 5.99930 20.5151 30.726
32 Ge 3P0 7.39944 15.93462 34.053
33 As “Sm 9.7337 13.5392 23.351
34 Se 3P: 9.75240 21.19 30.3204
35 Br 215,; 11.31331 21.591 35.3970
36 Kr 150 13.99961 24.35935 36.950
37 Rh 25”, 4.177130 27.23955 39.0
33 Sr '50 5.694355 10.99666 42.3335
39 Y 203,, 6.2171 12.2236 20.5244
40 Zr 311'2 6.63390 13.13 23.170
41 Nb 611),,2 6.753352 14.32 27.47
42 Mo "53 7.09243 16.16 27.13
43 Tc 5.5,” 7.23 15.26 29.54
44 Ru 5175 7.36050 16.76 23.47
45 R11 ‘sz 7.45390 13.03 31.06
46 Pd '3, 3.3369 19.43 32.93
47 Ag 2517: 7.576250 21.49 34.33
43 c4 15., 3.993323 16.90332 37.46
49 In 1p”; 5.736353 13.3703 23.04416
50 Sn 3P0 7.34392 14.63225 30.50260
51 Sb ‘5],1 3.60340 16.53051 25.3253
52 Te 31”; 9.0096 13.6 27.96
53 I “‘77: 10.45126 19.1313 33.0
 lonizau‘on PorcnriavaorAraI-m and Molecules 513

Table All
(continued)

Z Elemenl Ground level [P 1 (0V) 1.? [I (0V) [P III (0")

54 X0 '50 12.12904 20.9750 31.05

55 C0 251,2 3.093900 23.17 33.30
56 B0 '50 5.211665 10.00303 35.04
57 La 203,1 5.5769 11.060 19.1773
50 Ce 164 5.5306 10.05 20.197
59 Pr ‘!m 5.464 10.55 21.624
60 Nd 514 5.5250 10.72 22.1
61 Pm “Hm 5.554 10.90 22.3
62 5111 TF0 5.6436 11.07 23.4
63 Eu ‘51,, 5.67041 11.241 24.92
64 Gd 90; 6.1500 12.09 20.63
65 Th 571.5,: 5.0639 11.52 21.91
66 Dy 31., 5.9300 11.67 22.0
67 Ho 41”,, 6.0126 11.00 22.04
60 Er 3116 6.1070 11.93 22.74
69 Tm 257: 610436 12.05 23.60
70 Yb '5, 6.25394 12.104 25.05
71 Lu 20372 5.42509 13.9 20.9596
72 Hf 11', 6.02567 14.9 23.20
73 Ta ‘Fm 7.54957 16.2
74 w '00 7.06404 17.7
75 Re 533,2 7.03352 16.6
76 05 51:1,1 0.4302 17
77 [r 4199,, 0.9670 17.0
70 P1 3DJ 0.95060 10.563
79 Au 1517: 9.225520 20.5
00 Hg '50 10.43750 10.756 34.2
01 TI 112.,2 6.10029 20.4203 29.50520
02 P13 3P0 7.416604 15.032407 31.9373
03 13. ‘53,, 7.205519 16.69 7.5.563
90 Th 2P, 6.3067 1 1.5 20.0
92 U 51.5 6.09 10.6 10.9

Adapmd from Mon-1011. D. C 2000.71.17.15. 130.403: 2003.ApJS. 149. 205: and private conununicafion from D. C
Marlon.
514 Ionization Potentialsfar Mom: and Molecules

Table A2.2
Nuclear spins for common elemems

H D T 3He ‘He 11.1 ”c IJc "N ”N "o "o 130

11211;:11203120172117205120

13m 1331 2931 3031 “P 315 33s 14s 33'01 31c1 “K “'Ca “‘11
31201n01/2037203123723720 0

Table A2.3
Ionization potentials. dissociation energies. and heats of formation for molecules

LP. Do Proton nH LP. Du AH

Species (2V) (3V) affinity (eV) [Idlmol] Species (eV) (cV) (Id/ml)

H 13.599 2.69 216.0 H+ ... 1523.0

He 24.533 1.32 0.0 He+ 54.4 2372.0
c 1 1.266 6.46 71 1.2 C+ 24.4 1797.6
N 14.53 4.21 470.3 N+ 29.6 1373.1
0 13.613 5.03 246.3 0+ 35.2 1560.7
3 10.360 6.31 274.7 3+ 23.4 1272.0
Mg 7.644 3.03 146.5 1913+ 15.0 334.2
51 3.152 3.63 446.0 31+ 16.3 1233.0
Fe 7.37 414.0 Fe+ 16.2 1173.0
HeH“ 1.32 1352.0
H2 15.43 4.43 4.3543 0.0 H; 16.3 2.63 1433.3
H; 1 107.0
CI 12.0 6.21 7.20 317.0 c; 5.32 1992.0
czH 1 1.6 7.30 560.0 C2H+ 1639.0
c214,+ 1323.5
N; 15.53 9.76 5.03 0.0 151; 3.71 1503.3
N1H+ 1035.5
01 12.06 5.12 4.340 0.0 o; 6.66 1164.7
0114+ 1103.5
cJ 12.1 NIA 331.0 c; 2004-0
C3H+ 1593.0
CH 10.64 3.47 7.59 592.5 cm 4.09 1619.1
CH2 10.4 3.63 390.0 CH,+ 1336.0
 Ionization Potentials for Atoms and Motecules 515

Table 4.2.3
{continued}

LP. Do Proton 13H 1.11. Do 3111

Species (3V) (3V) affinity (4V) (Ufmol) Species (3V) (2V) (Idlmol)

CH3 9.33 5.55 149.0 CH; 1093.0

C11. 12.55 4.4 5.63 —66.3 CH4+ 1140.0
CH"; 905.0
(:0 14.01 11.9 6.20 —1 13.3 co+ 3.34 1233.3
11cc 9.33 6.72 44.3 Hco+ 325.6
Hzco 10.33 7.24 — 104.7 H2C0+ 944.5
HJOO+ 703.0
(:02 13.79 5.45 5.51 —393.1 C02+ 935.7
11130; 539.0
CN 14.17 7.3 4.99 436.3 CN+ 4.35 1796.3
HCN 1359 5.6 7.37 135.5 HCN+ 1443.0
HCNH+ 947.0
CCN 12.0 556.0 CCN+ 1715.0
Gem-1+ 1531.0
cs 1 1.34 7.36 3.2 262.0 cs+ 6.33 1356.0
HCS 310.0 Hcs+ 1013.0
11,133 9.33 105.0 Hzcs+ 1006.0
H3C$* 901.0
ocs 11.2 6.51 - 142.0
NH 13.1 3.2 6.12 376.5 1411+ 73.39 1673.1
N112 11.4 7.93 191.6 NH; 1266.4
N113 10.15 4.3 3.93 439 NH; 941.0
1411-1;r 630.0
N0 9.7.5 6.50 4.99 90.3 140+ 10.35 934.7
HS 10.5 3.6 7.16 136.5 118+ 3.5 1137.0
1125 10.46 7.37 — 17.6 1115+ 991.0
1135+ 797.0
so 10.29 5.36 5.0 50+ 5.43 1000.7
50; 12.35 6.97 —294.3
SN 4.3 263.0 514+ 6.3 1119.0
S'1H 7.9 3.1 >10 374.9 5114+ 1136.2
3114; 1155.2
810 “.43 3.26 NIA — [01.6 SiO“ 5.0 1001.2
516 Ionization Potential:for Atom and Molecules

Table A2.3
(continued)

|.P. Do Pmlon AH LP. Do AH

Species (eV) (eV) affinity (eV) (Uhnol) Species (eV) (eV) (thnol)

SiC 734.7 SiC+

HSi.C+
stiC+ ...
OH I3.0 4.39 6.25 38.4 OH“' 1| 1292.?
H10 12.61 5.1 l 7.16 —233.9 H20+ 977.9
{130* 597.0
CH..N+ 745.0
CH3OH 10.33 7.3l ~190.7
c2}!2 I 1.41 6.59 213.6
52 9.36 4.37 128.3 5'; 5.37 103L0
APPENDIX 3

List ofInterstellar Molecules

Table A3.l
Inorganic species

Diaiomic 'n-iatomic

H2 (molecular hydrogen) PN (phosphorous mononitride) H10 (water)

HF (hydrogen fluoride) AIF (aluminium fluwide) HNO (niu'oxyl)
C0 (carbon monoxide) NS (nin'ogen sulphide) H25 (hydrogen sulphide)
SiH (silicon hydride) T10 (titanium oxide) C01 (carbon dioxide)
NO (nitn'c oxide) NaCl (sodium chloride) N20 (nitrous oxide)
HS (sulphur hydride) SiS (silicon suphide) NaCN (sodium cyanide)
HCI (hydrogen chloride) AlCl (aluminium chloride) MgCN (magnesium cyanide)
SiN (silicon nitride) FeO (iron oxide) AINC (aluminium isocyanide)
CS (carbon monosulphide) KCl (potassium chloride) OCS (carbonyl suphide)
SiO (silicon monoxide) 802 (sulphur dioxide)

Four atoms Five moms

NH, (anunonia) Sil-L; (silane)

517
518 list ofInterstellar Molecule:

Table A32
Organic molecules

Alcohols Aldehydee and ketonu Acids Hydroouhum

CH30H (rrlethnnul) H2C0 (formaldehyde) HCN (hydrogen cyanide) CH. (meflune)

C2H50H (ethanol) HzCCO (ketcne) HNCO (isocyenic acid) CIR; (acetqun)
CH1CHOH (vinyl alcohol) CH3CHO (aoetnldehyde) HCOOH (formic acid) 01H. (ahylgng)
HCfll-IO (propynal) CH3COOH (acetic Icid)
CH300CH3 (acetone)

CH20HCl-IO (glycol-aldehyde)
CHICHCHO (propenal)

Amine and emida Esters and ethers Drama-sulfur

CH3NH; intelhylamine) CHJOCH3 (dimethyl ether) H3CS (dtiofonmldehyde)

NHZCN (cyanamide) CHJOCHO (methyl female) CH38H (methyl merupten)
NHZCHO (formunick) CH3OC2H, (ethyl methyl ether) HNCS (thioisocyanic acid)

Paraffin derivatives Acetylene derivatives Other

CH3CN (methyl cyanide) CH3CCH (methyl acetylene) H1CN (melhylene amidegen)

CH3CH1CN (ethyl cyanide) HCJN (cyanoacetylene) Cl'lle-l (methylenill'line)
CHZCHCN (vinyl cyanide)
NH3CH-2COOH (glycine)
 List of Interstellar Molecules 519

Table A3.3
Unstable molecules

Radicals Ions

CH (methyladyne radical) SiCN (silicon cyanide) H; (protonalnd dihydmgcn)

CH2 (melliylene radical) HCS (lhioforlnyl radical) CH+ (medlylidyne ion)
CH3 (methyl radical) SO (sulphur monoxide) H30+ (protonaled water)
NH (nitrogen hydride) C¢H (butadiynyl radical) C0+ (carbon monoxide ion)
NH! (aminyl radical) CJN (cyanoelliynyl radical) HCNH+ (protonaled hydrogen cyanide)
OH (hydroxyl radical) H2CCCC (butauienylidene) HCO+ (fonnyl ion)
C; (dicarbide) C30 (u-icarbon monoxide) N2H+ (prolonated nitrogen)
C1H(elhynyl radical) C28 (C28 radical) HOC"' (hydroaymethylidyniurn)
CN (cyanogen radical) C5 (C5 radical) H300+ (protonalnl fonnaldehydc)
HCO (l'onnyl radical) C5H (penlynylidyne ndical) HCS“ (Illioformyl ion)
C3 (C3 radical) SiC3 (SiC; radical) l-IOCO+ (protonaled carbon dioadie)
C4 (C4 radical) C35 (C38 radical) SO+ (sulphur monoxide ion)
l-C3H (propynl radical) Cal-l (hello-iynyl radical) H2C3N+ (prolonaled cyanoacetylene)
HICCC (propadienylidene) C5N (cyanobuladiynyl)
HCCN (HCCN radical) C6H1(hellapentaenylidene)
HC..N (HC4N radical) C50 (050 radical)
C10 (dicarbon monoxide) SiC4 (SiC4 radical)
CH2CN (cyanomell'lane radical) C7H (C1H radical)
SiC (silicon carbide) C3H {CsH radical)
CP (carbon monophosphale)

Rings Carbon chains lsomors

C'CJH. (propynl radical) CH3C.H (melhyldiacetylene) HNCGlydrogen isocyanide)

c—C3H1 (cyclopiopenylidene) CH3C3N (melhylcyanoacetylcne) CHJNC (molllyl isocyanide)
«Cal-I40 (ethylene oxide) HC5N (cyanobuladiyne) MgNC (magnesium isocyanide)
c-SiCz (silicon dical'bide) HC1N (cyanobcxu'iyne) HCCNC (isocyanoacelylene)
Cal-l6 (benzene) HCgN (cyanooclalecrayne) HNCCC (cyanoacetylene isomer)
HC. .N(cyanodec-apcnlayne) SiNC (silicon iaocyanide)

Adlpwd from Tilmer 1989. So: also the [in of inlerslellar moleculea by A. Woollen. hnpu'fwww.cv.mm.¢dul~lwcntlenllllmola.btnll.
APPENDIX 1

Solutions to Selected Exercises

Chapter 2
I. By setting Bum/31L) = 0, we have

12' _
4. (A4.l)
eI—l

The nonlinear equation has a root of 3.92. Subsrituting this value of 1 into
d
A3A=-l—55aT4( I ) (A42)
11' e‘ — l

we have

(1mm = l—ia 1"(433)

11'

= 0.234.:1‘. (A43)
Since FA = 33*. (1mm = 0.736aT‘.
2. From eq. 2.74

1 °° .
[(0. u) = —f (a + bt)e"”‘dt
1‘ 0

; a + bu. (A44)
Using the definition of mean intensity (eq. 2.20) and integrating over only the
upper hemisphere (9 = 0 —> Ir/l), we have

1 2!! 51/2
J=— emf (a+bcosfl)sin6d9
2n 0 o
b
= (a + 2)
_ . ( A45 )

521
522 Solutions to Selected Exercises

Similafly for the emergent flux.

n12
F+ :2!!! (a +bcosfi) sinecosodfl
o

= Ir (a + %) . 04.4.6)

(3) 1(9) = to /1- :9}.

II
(b) From eq. 2.73.
I'

l('r. p. = 1) =1 e"(a + bx)dx

0

= (a +b) [1 — e"'] - bu"

l(0)=(a+b)[l— e"°'W9]bzm/1—91/9="W"99195

(A43)

(c) The total flux can be found by substituting eq. A43 into

an
F =21! j [(0)0d0. (A43)
0

‘Mth a change of van'able y = ‘l l - 02/92, eq. A43 reduces to

I I
F = 21:93 (a + b) j (1 — e"°’)ydy — bro I yze'm'dy
o 0
(A43)
= 7:93 [(0 + 3b) (fie—'0 — 32H — e'°]) + (a + b + 2be"°)] .
to to

(d) When to -> on,

F = 1:950: + b)
FmA = n902 Hm AGO4 K)

= 905 Jy, (A4.IO)

. The electron density in the nova envelope is

n, = M (NH 1)
41rr2VmH '
 Chapter 2 523

and the absorption coefficient is x = n.0,. Defining the optical depth at the edge of
the envelope (R = Vt) as 0. we see that the optical depth at radius r is

W '
o— r(r) = -1 ,-
fl 1’.
417 Vt?!" r1
(A4.12)
The radius at optical depth 2/3 is therefore
—I
r = —'— + §"‘.’_"'u . (A4.13)
Vt 3M0,

For M = 10':I Mo yr". V = 2000 ltrns", t = lday. the outer edge ofthe envelope
is 1.7 x 10” cm and the r =2/3 surface is at r =3 3: to” cm. From «1.2.61.
Tefi=4700Katr=ldayanddocteasestoBfiOOKatt: lOdays.
s. The luminosity ofa staris ”Dir. where F = not, — t.) or F = F,(v| — v1) for
the two stars in question. The efiective temperature is [DZF/ Rzarl‘, and has values
of 1.7 x 10‘ and 1.8 x 10‘ K for the stars A and B, resPectively. In spite of the similar
effective tempemtures. the two stars have difierent colors. Star A emits relatively more
flux at shorter wavelengths than star B and would appear bluer.

6. The heating rate of the planet is given by the solar flux at distance 0 times the cross
section of the planet:

L
r: 0 (m1). (A4.l4)
41:42
If the planet radiates like a blackbody, the cooling rate is

A = aT‘(4rrr2). (MIS)

By equating the heating and cooling rates.

14
r=< Lo )’
115mm2

278.3 K
= W. (A4.l6)

Taking into account q and x.

273.3 K 1— a 1"
= (ti/AU)”: ( x ) (Mm
For a slow rotator. it is always the same side that is heated by the Sun. The
radiating surface ol‘the planet is therefore 2m2 instead 01’4an as in eq. A4.15.
524 Solutions to Selected Exercises

7. From eq. 2.50 and the Wien approximation.

w=V€
2562 -h c,ur . (A4.l3)

we have

% .—_ r’W/“T. (A4.19)

Since the maximum of BA is at Ira/MT = 4.965.

B -BBw = €4.9asitmlt.
(A420)

For (B — Bun/B < 0.3. we have )t < 4.12).“. So the Wren approximation is accu-
rate to 30% up to 4 times the peak wavelength. For the Rayleigh—Jeans approximation.

3—3, e"'9‘mw“—I — l. (A420

B ' 4.9esAm/t
For 30% accuracy. .1. > 9.36).“. Therefore, the Wien approximation describes most
of the blackbody shape (from A = 0 to 41“,“). whereas the Rayleigh—Jeans approxi-
mation is valid only for the far tail. starting at almost 10 times the wavelength of the
maximum of the Planck function.

Chapter 3

For a square filter profile of width A}. = A2 — Al, 41)., = I/(u, - v2) for 1: between v1
and v2 and zero outside of u. and 1);. Define: = v/vo. y = hu/kT. :0!) = y3/(e-" - 1).
then eq. 3.4 can be written as

K _ If; z(y)dy/[2(yo)(yu - y2)l

A422
L? :"dx/(Jtl — :2) ( )

For 1.0 = 12. 25. 60. and 100 pm. with the respective AA of B. [0, 40. and 40 pm.
the values for K are 1.40. 1.13. 1.42, and 1.13. respectively.
From eq. 3.10.

F. = 11923.0». (A423)
we have Tb = 1.76 x 106 K.

a
TA =f Towed“ thzlnzhflpdp. (A4'24)
o n' 32
 Chapter 3 52.5

For To = 1K. B = 1.2. 3. 5. and 10". TA = 0.94. 0.5. 0.27. 0.1]. and 0.03 K. respec-
Evely.
Substituting eq. E13 into eq. 3.36. we have

2!
Wm = JK (So. (A425)
F0
where

m 2
K61.) = f e‘” man-M) d¢ (A426)
0

and a = In 2/401. Diffemnfiating eq. A426 w.r.t. S1 and perfonning integration by

parts. we have
CD
i=1] 1.3.54“ Mensa) 44
0'81 0 0

= 2:: 1 SA K_
_
(A427)
0

Equation A42? can he integrand to give

mm = K(0)e"'"§/°. (A423)
Since

m 2
K(0) = f 2-“ mp
0

l n
= 5 —, (A429)
6

we have from eq. A425

2
V062) = %0 Eflie-wwv ‘" 1’53. (A420)
The total flux of the source is

F0 =1.
m I08
-(In 2mm! d¢
—oe

1! w2
= to —--. (A431)
I112
526 Solutions to Selected Exercises

Substituting eq. A4.3l into eq. A430, we have

V0091) = e-(fl'iwz/ In 2:”:-
(A4.32)

Therefore v0 = i at 51w =10 2/3. Expmsing L in units and and win mm,
we have L i w = 45.5.

The intensity distribution of the two sources is equivalent to the difference of two
sources of size a = a + L and at = L —- a centered at 1 = 0. Using eq. 3.37. we have

_sin(21rSA("+")) _sin(2nsi(£§—"D
V° (5 211$($.32) 2nsl(£§—‘) ( A433 )
Substituting eq. 3.3? into eq. 3.34, we have

[(99)-
— 2—170
Ira/0“” 00507:x)— dx, (A434)

where x = rrSla/Z and m = 290/0. Form < l. the definite integml above has a value
of rr/Z. Since this condition applies in the present ease, I (00) = Fo/a.
B. The first zero occurs at S; = 1/0. Therefore a = 1.2 x 10""l radians or 25 arcsec.
A five-element array has C5 = Sl/3t2!=10 baselines. A five-element minimum
redundancy linear array can be constructed with five antennas with spacings of
IL. 2L. 4L. and SL between successive antennas. This gives a total of 10 baselines
of l. 2. 3. 4. 5, 6, 7. 9.1].andlZL.

Chapter 4

I. The ground-state electron configuration for carbon is Is2 252 2p2. The spin and orbital
angular momentum quantum numbers for the two valence electrons are s = 1/2 and
8 = 1. respectively. Under b—S coupling. the allowed total spin angular momentum
quantum numbers are S = 0 or I. and the total orbital angular momentum quantum
numbers are L = 0 or 1. Under Hund‘s rules. the higher 5 and L have lower energy.
The ground state is therefore 5’ = l and L = l, or 3.P. The possible values for the
total angular momentum quantum numbers are IL — SI -) IL + SI. or J = 0.1, and
2. Since the outer shell is less than half-filled. the lower J have lower energy. The
ground state is therefore 3P0.
By making a change of variable y = nx. we have
on 1.2 d
G(x I ) =fll 8' x

no l co
= z: — f yze"dy_ (A435)
113 ,.
 Chapter 4 527

This integral can be evalualed using integralion by parts:

on

f yze'My = e'wyf + 2y. + 2)

Y!

= e"""(r|2.x12 + 2111. + 2). (A436)

Substituting back into eq. A435. we have

“I: + 2n. + 2). (.4437)

n-l

Making useoflheideutiljes f‘” y" 'f’dy: l"(a) amigo): 3:.J,.wc have

CD 12
FUN) = 6(0) =f (11
a 21—1

=Z—13f” y26'”)
"i=1"

= C (3)113)
= 2(0). (A433)

Making use of the definition of the Bernoulli numbers

10 It k 1

[a ( °°as] ”)‘h—x”
I! [k 2(k+ 1) +2(2n+k)o(2n)!] (M39)
_ I—l
Ml! Zp“” k: 1. 2, 3,... (44.40)
B“ = at)” p=1

1-1 51”
=12[2 6 +2?”me

z l
_-_I+Bz__12'_1;3616
... 4.41
’[2 6+ 4 +6-4'+86!+ ] (A )
528 Solutions to Selected Exerciser

Looking up the values of 51. B... and so on from mathematical tables. we have

l I l 1:2 I x‘ l 16
F = 1 -_.. - __ __ _
o") I [2 6+(6)4-2!+( 30)6-24+(42)8-720+ ]
1 l l x2 x4 x6 :1
= — — - + —- — — +
I [2 6 43 4320 24l.920
z l J: x2 14
2 __...+__._.___ A442
‘[2 6 43 4320 ( )
This approximation is accurate to 1% for :1 up to 2.83.
From eqs. 2.41 and 4.26. we have n(2)/rlH = 2 x 10-10. 3 x 10-5, and 5 x 10-3 for
T = 5000. 10.000 and 20.000 IL respectively.
From «1.4.27. we have x022) = 4.7 x 10"22 crn‘I and dig) = 2.3 x 10'22 cm".
The mean free paths for photons at 02 and v; are 682 pc and 1.4 kpc, respectively.
The number of BO stars needed is given by the ratio of their respective Lyman con-
tinuum output. For the BS star. 600.01!) K) = 0.209. compared to 6012.000 K) =
0.557 for an 05 star. Using eq. 4.56 and their respective luminosities. we have
Q = 1.0 )-:10“'8 sec" for no and Q = 5.lx10‘9 sec" for the 05 star, givinga ratio
of 29.

Chapter 5

The quantum numbers ofthe electron in the first excited state of H are 5 = #2. l = 0. 1.
so that possible electronic states are 225m and 22 P1.f2.3/2- The degrees of degeneracy
for these three states are 2. 2. and 4. respectively. giving a total of 8. Since the
ground state of H is 128.”. the only allowed transitions are 22?”; — 123m and
22F”: - PSI/2. From eq. 5.13. the source functions for these two transitions are
0.025 and 0.012 erg cm": s-l Hz- ', respectively.
Since these are doublets, the multiplicity is 2. or S = 1/2. The possible values for J
are IL — sl —> u. + 5|. so the levels are 2pm... and 203,251., Since AJ > l for
2P1]; — 205,2. this transition is forbidden. The relative strengths of the transitions
for this multiplet are as shown in Table A4.1.
From the sum mle. we have x + y :0.6 = 2(3/2)+ l 12(5/2) + 1 =4 :6 and
x :y + 0.6 = 2(l/2) + l :2(3/2) + l: 2 :4. By solving these equations. we have
x = 0.33 and y = 0.066.
From eq. 5.45 and 2.33. the absorption coefficient is

2
a = (l _ e—hv/H’) %fji¢v' (A4433)
 Chapter 5 529

Table A4.1
Relative strengths of the
multiple! 11° — 20
2D

1/1 5:2 3;:

2P 3/2 0.6 y
117 0 x

The width of the square profile is Av = (A V/c)v = 4.7 kHz. Since it“ = l/Au =
2.1 x 10" see. a has a value of2.2 x 10"9 cm2. The Optical depth is
r = nH(2R)a
= (10 cm")(2 pc)(2.2 x 10'19cm2)
= 6.7. (A444)
. The degrees of degeneracy for tlte two states are 3; = 2012) + I and g; = 20/2) + l
for 2P3]; and 2P1”, respecuvely. The energy separation (E) of the two States is
hell = 0.097 eV. Substituting the values of T. E. 3.. and 912 into eq. 5.l21. we
have C12 = 7.1x 10‘9 cm3 5‘]. From eq. 5.123. C2] = 1.3 x 10‘8 cm3 s". From
eq. 5.125, the populatiori ratio 112/”; is 3 x 10".
Substituting eqs. 4.33 and 4.39 into eq. 4.41, we have

eliafnz on e—x
11,,(10‘ K): (3.3 x 10‘”) —— — — d; cm3s '. (A445)
11’ Isami I

which gives an =19.5.851.432.107.209. 1.50. 1.12. 0.36. 0.67.and 0.54 x 10‘”

cm3 sec 1 for n = l . . . 10, respectively. Summing over it from 1 to 10. we have
GA = 4.27 x 10‘'3 cm3 sec" for Case A. Summing over it from 2 to 10. we have
a, = 2.32 >(10‘l3 cm3 see" for Case B.
. From the equation of statistical equilibrium. we have

"fit _ 31:01:] + Bu} + CU)

_ (114.46)
”1'31 3j(3ji-’ + C11)
Maldng use of the relations in eqs. 5.8, 5.9. and 5.123, we have

. .
",3; = Bu(Tk)(e hit/ITI _
1+ Ae bv/ltT* + J)_
_
“4'4,”
mg,- i + 43.41,)
530 Solution: to Selected Exercises

Substituting this expression into eq. 5.12, we have

5v-_i+Am
1+A (A4.43)
10. Si w M933. 945 A, 0 w 111031, 1037 A, N v 10.1233. I242 A.

Chapter 6
I. See Figure A4.1.

2. 1hedominantopacityatl=05andlumisb—f.andthetolal optical depthsare

011133 and 0.008, respectively. At 1 = 1 cm, the dominant opacity is f—f. and the
optical depth is 2 x 10". Since the cloud is optically thin at these wavelengths.
the total flux emitted is directly proportional to the emission coefficient and can be
calculated with eq. 6.22.
log I; (cm")

i:

_l_ I lllllll I I I I
102 1 343513103 1 intiliiloll
Wavelengdltllt)
Figure A4.1
Absorption coefficient of H at 5000 K.
 Chapter 9 531

Chapter 7

1. From the equation of statistical equilibrium (eq. 5.147) and the relation between
collisional coefficients (eq. 5. I23)

I
=-——T + It 7;. (A4.49)
I
l+q no 1+1:

where n = 355.- Efigfl. Under high density and kinetic temperature (rt >> I). the excita-
tion is dominated by collisions and T, —> TX. At low densities (n r-r O). tlte excitation
is dominated by stimulated absorption and emission, and T. -> Tag.
The statistical weights for the rotational states of H; are (2! + l)(2.! + i). For odd
values of J. I = I. therefore 3 = 9. 2t, 33. and 45 for J = l, 3. 5. and 7. respectively.
For even values of J. l = 0. therefore 3 = 1. 5. 9. and 13 for J = 0. 2. 4. and 6.
respectively.
The nuclear spinof 110 is 5/2. The possible values for F are 5/2 for J = O, 3/2. 5/2. and
7/2 for J = l. and “2. 3/2. 5/2. 712. and 9/2 for J = 2. The number of hyperfine lines
are 3/2 —> 5/2. 5/2 -> 5/2. and 7/2 -> 5/2 for J = l—> 0. and 9/2 -> 7/2. 7/2 —>
7/2. 5/2 —> 7/2. 7/2 —-> 5/2, 5/2 —> 5/2, 3/2 —> 5/2. 5/2 —> 3/2. 3/2 —> 3/2. and
l/2—> 3/2forJ=2—> 1.
Since F=J + land} =N +L+S.thehyperfinestatesforJ= ll/2andJ =9/2
are F = 13/2. 11/2. 9/2 and ”/2. 9/2. 7/2. respectively. Since there are two A
doublet states + and —. there are two pairs of triplets F = 9/2 —> 7/2. [3/2 ->
“/2, [1/2 —-> 9/2.

Chapter 8

1. The symmetric stretch v, is not infrared active.

Chapter 9

l. The statistical weights of the rotational levels are 2.! + l. or 3 and 5 for the J’ = land
2 states. respectively. The energy separation between the two states is 2hBUj + l) =
2ft(50 GHz)(2) = 1.3 x 10—15 erg. From the definition of the excitation temperature
(eq. 9.13). we have

ln(n2/rt.) = ln(5/3) — 12/”... (A450)

which gives ’I‘Jr = 6 K. Similarly. from the definition of the departure coefficients
(eq. 5.110).

ln(n2/n.) = ln(5/3) + ln(b2/b.) — E/ ka. (A451)

which gives bZ/bl = 0.524.

$32 Solution: to Selected Exemises

For a uniform profile of width I MHz. fem cpvdv = 1 implies that on = 10‘6
see over this width and zero elsewhere. Making use of eqs. 5.9 and 5.15, we have
a” = 1.2 x 10-” cm‘z.
3. At high temperatures. almost the entire rotational ladder will be excited. and the
summation of the partition function (eq. 9.6) can be approximated by an integral:
00
Z(T) = f (21 + 1)e""’m+”’"dt (A452)
0
letx = JU +1).th = (2.! + Dd]; we have
W
2(7) ___f e—hslftTdI
o
_H_
_hB
21:?"
= . (A453)
h U10

For T = [00 K. the partition function for the rotational ladder of C0 is 36.486.
The above approximation gives a value of 36.15.

Chapter 10

1. From eq. 10.17,:14 =1.2 x 10-9. Using eqs. 10.13 and 1019. we have A3 = 7.].
AV = 5.0, A, =14, A, =1.5,AH =0.97, and Ax = 0.63.
2. 1m = 0.2891 _s_5 cm
a+ '

3. Sinner: = 0.a = 1, Q0 = 1. and L0 = l um,eq. 10.31 gives IN) = 1250(r/5R.)‘°"

K. From eq. 10.18, :01) =0.036(A/,um) ". Defining x = r/R,. we have from
eq. 10.33

__ no 2 1 fl 5 10.080 1 2dz
AF; — 30——D2 (th )Nd ( A ) f1 ——_e(6.05umf»\)I°-‘
_ 1' (A454)

where
0.1M?
Nd = 4—;1'” (A455)
3"“ 1’:

is the total number of dust grains in the cloud.

4. For a blackbody radiator of temperature I}, and size a at a distance of D from Earth.
the total infrared flux emitted is
T 2 4
Fm = (21)) "_d_ (A456)
J'I'
 Chapler 15 533

Table A4.2
Solution to the Lane-Emden equation

n {I nor/:5

0 14494 1.0000
0.5 2.1523 1.8361
1.0 3.14159 3.23987
1.5 3.65375 5.99071
2.0 4.3528? 11.40254
2.5 5.35528 23.40646
3.0 5.89685 54.1825
3.5 9.53581 152.884
4.0 14.97155 622.403

From eq. 10.42. the equilibrium temperature is

Td= [(1 _ "’3 (1-H 1/4 1;. (A457)

4 1'

Substituting eq. A457 into A456. we have

F = (I “ w) 2 L.
—. 4.58
IR 411D2 (”a )41rn'2 (A )
Adding eq. 10.41 to eq. A458. we have

_
Fvis + FIR — (3:72- Lo 1'1'0 2 4ND:1 . (A459)

Chapter 15
See Table A42.
The equafion of motion is

m'r' = — 05:”. (A4.60)

r
If we write F = child! = (du/dr)(dr/dr). eq. £14.60 can be integrated to give

3m»2 = GMm (1 — 1). (A461)

2 1' To
53-4 Solutions to Selected Exercises

after applying the initial condition I: = 0 at r = r0. Setting u = dr/dt. eq. A46! can
be written as

a f
(it = dr (A452)
26M r0 — r

Lettr=r0cos2 9;eq.A4.62 canbeintegratedtogive

2 ————s'n20
t: l— a 1 "° . A463
(ml: NHL... ( ’
Applying the boundary conditions t =0. r = re. and 9 =0 and t = tf. r = 0. and
6 = 1r/2.

11' I 2 3/2
If = (—4) ——r0 . (A464)

ForM=1M0.r=lpc.tf=1.66x 105yr.
From eq. 15.76. p0 = 1.4 g cut—3. Substituting into eq. 15.30. we have a flee-fall time
of 0.5 hr. Dividing the total self-energy of the Sun (eq. 15.73) by Lo, we have a thermal
(or cooling) time of 20 million years. The fact that the dynamical time is much shorter
than the thermal time implies that the Sun can adjust itself dynamically very quickly
in response to thennal changes and therefore remains in hydrostatic equilibrium.
Since x., or v-2 (eq. 6.25). the optically thick surface is larger at lower frequencies. If
the wind has an outer boundary. the spectral index at low frequencies will be steeper
than 0.6 as given by eq. 15.107.

Chapter 16
1. From the definition of sound speed (eq. [5.21).
2
M2 _
_ 391% . A465)
’ 5P1 (
For a strong adiabatic shock. P. = gpoug. uo =4u.. and p1=4po. therefore M} =
0.2.
From eqs. 16.28. 16.30. and 16.36. R = 14.1pc. R = 553 inns". and T =7 x 10‘s
K. The amount of interstellar gas swept up by the shock is M = g7! R3po. Fora strong
adiabatic shock. p. = 4p... Equafing the mass in the swept-up shell M, = 4n RZARp,
with M. wehave AR/R = 1/12. Fromeq. 6.31. therateofenergy loss byf—femission
is 7 x10“5 erg 5‘1.
Symbols and Abbreviations

a the fine—structure constant

a polarizability (cm3)
a,,¢(T,) recombination coefficient at temperature T, (cm3 s“)
aA413 Intel recumbinntion coefficient under Case A and B (er-13 5“)
tr’ the rate of populating a state by direct recombination or cascm'le (cm“3 s")
are“ effective recombination coeflicient {cm3 s")
1" heating rate (erg ctn‘3 s")
l" ratio of the radiative to gravitational foece
y the adiabatic index. given by the ratio of specific heats
y clamping constant (5")
A9 fringe displacement
AV line width nuns")
e filling factor
6 energy efficiency
6 dielectric constant
9 angular radius (radians)
it, absorption coeflicient (cm")
A cooling rate (erg cm'3 s")
J. wavelength (cm)
pt 0059
u electric-dipole moment (esu cm)
it reduced mass [3]
,u mean atomic weight per 1-! atom
u' mean atomic weight per particle
11, mean atomic weight per electron
u frequency (Hz)

Those without units attached are dlrrnnsionless quantifies.

S35
536 Symbols and Abbreviations

wavenuinbcr (cm—l)
vibrational modes of a polyatomic molecule
pl density or dust particle (g cut-3)
P: density of swept-up shell (3 col—3)
density of the general ISM (g cm“)
pa density ofthc bubble (g Ora—3)
Stephan-Boltzmann constant (5.67l 10" erg cut—2 5-1 K“)
collisional cross secticm (m1)
recombination cross section (cm!)
optical dcpvh
normalized line profile for absorption (l-lz")
filter profile
gravitational potenlinl energy (erg)
collisional strength
solid angle (sterodian)
scattering angle (radian)
normalized line profile for emission (Hz")
spontaneous emission coefficient 6")
total extinction at V band. or visual extinction
radius of dust grain (cm)
total atonlic absorption coeflicient (crn2 s"l )
the Bohr radius (0.529 10-“ cm)
speed of sound (loo 5“)
atomic absorption coefficient (cm2 s"1 Hz")
Planck function (erg cm"2 s"I slcr'I H1")
rotational constant (Hz)
beam size (arcsec)
stimulated emission and absorption coefficients (c1112 erg" 5“)
color index
critical impact parameter (cm)
departure coefficient
collisional rites (cm‘3 s")
ndsoqnion energy (erg)

centrifilgal distortion constant (Hz)

mtivation energy (erg)
the potential barrier against surface migration (erg)
kinetic energy per volume (erg cm")
 Symbols and Abbrewial‘ians 537

total energy per volume (:3 cm”)

amount of energy released in a supernova explosion (erg)
color excess
averaged kinetic energy of the ejected electron (erg)
monochromatic flux (erg crn'2 s‘l Hz")
integrated flux (erg cm'2 5")
total flux over a filter (erg cm"2 s‘l)
oscillator strength
oscillation frequency of an adsorbed particle in the adsorption potential well (Hz)
Maxwellian distribution
gravitational constant (6.63 19-5 dyne cm2 3‘2)
beam profile
statistical weight
the Gaunt factor
hydrogen
first moment of intensity (erg cm'2 s‘I Hz'I ster‘ 1)
Planck‘s constant (6. 626 10"” erg s)
helium
spcific intensity (erg cm"2 s'I Hz" ster")
average intensity (erg cm": s‘l Hz" Stet")
intensity of cosmic rays (proton cm"2 sec'l stead" Gev“)
upper and lower states of a (H!) transition
rotational quantum number
mean intensity (erg cm’2 5" Hz" ster")
mean intensity across the profile of an emission line (erg cm‘2 s"I Hz‘l star")
flux unit (IO—’3 ergcm‘1 5‘1 Hz")
emissivity (erg crn'3 s" ste'r'l Hz")
integrated emissivity (erg cm‘3 s" ster")
quantum number for rotational states of a symmetric molecule
second moment of intensity (erg cm'2 s'I Hz" ster")
quantum numbers for rotational states of an asymmetric molecule
the Boltzmann constant (1.38 10'16 erg K‘l)
rate constant (cm1 s'1 for two-body reactions)
radiative recombination coefficient (con1 5")
quantum number of a free state
imaginary part of the complex index of refraction
baseline between two elements in an interferometer (cm)
538 Symbols- and Abbreviations

“iflaaaz-aSFE-KI‘FKth
solar luminosity (3.826 1033 erg s-')
orbital angular momentum quantum number
quantum number associated with vibrational angular momentum
Mach number
5. Jean‘s mass (:1
mass loss rate (3 5")
solar mass (L959 1033:)
mass of swept-up shell (3)
absolute magnitude at wavelengih A
apparent magnitude at wavelength A
complex index of refraction
principal quantum number
fringe order
real part of the complex index of reflwion. or refractive index
polyu'opic index
electron density (and)
up proton density (cm-3)
I1 1 number of degrees of freedom
nH total H density (em'J)
P pressure (dyne cm‘z)
PW) scattering phase ftutctiort
Pate] beam pattern
p dipole moment (rsu cm)
p probability of dissociation
pa momentumoflheshetltgems")
pt: patsec(3.036 10'8 em)
Q Lyman continuum photons emission rate (photons s")
QA extinction efficiency
R production rate of gas-phase reactions (cut'3 5‘ ')
R; photoioniution rate {s")
ac“ cosmic ionization rate (r1)
RN photodissoeiaiion rate (5")
R a generalized alkyl group (e.g.. methyl. ethyl. propyl. etc.)
R, Jean's length (cm)
kw evaporation rate (sec-l}
Rat-h molecular formation rate on surface 0! grains (em3 sec")
R.“ rate for a surface molecule to sweep over the entire surface of a grain Gee")
 Symbols and Abbreviations 539

RV ratio of the total extinction and color excess

ROI. 8) radial wavcfunction with quantum numbers n and 3
source function (erg cm"1 541-12" stcr“)
anay spacing
kinetic energy per unit mass (er: s")
amenna temperature (K)
brightness temperature (K)
temperature of the bubble (K)
dust temperature (K)
kinetic temperature of electrons (K)
radiation temperature (K)
excitation temperature (K)
frwfall time (3)
internal thermal energy (erg)
internal energy per volume (erg cm")
inlanal energy per unit mass (”8 8"]
velocity in the frame of tererente of the shock front (cm s")
radiation energy fiensity (erg urn"3 Hz“)
volume (cm’)
visibility function
velocity (cm 5‘ ')
vibrational quantum number
tenninal velocity of the stellar wind (cm s")
drift velocity (cm s")
line-of-sight velocity (cm s")
infall Velocity (cm 5")
velocity of local standard of rest (cm 3")
equivalent width (H1)
equivalent width (cm)
albedo
ratio of electron to proton density
sticking coefficient
nuclear charge
partition function
Glossary

ab initio In contrast to the sentiempirical approadr to the computation of

molecular strucmres. the ab initio approach proceeds from first
principles (the Schrodinger equation) and makes no use of experimental
data in the calculation.
AFGL Air Force Geophysical laboratory
A03 asymptotic giant branch stars
A13 aromatic infrared bands
ALMA Atacama Large Millimeter Array
alcohols cornpnunds with hydroxyl (OH) groups bonded to saturated .rp3 carbon
atoms. Alcohols can be thought of as organic forms of water in which
one H atom is replaced by an organic group.
aldehyde compounds containing the —-CH0 functional poop
a family of molecules consisting of C atoms joined by C—C single
bonds (ea. mm, CH4: mm Calls)
alkyl group the partial structure that remains after an H atom is removed from an
alkane (c.g., removal of H from methane gives a methyl group ——CH3)
alkenes hydrocarbons that contain a C-C double bond (e.g., ethylene 9H4)
hydrocarbons that contain triple bonds (e.g.. acuylene)
aliphatic compound organic molecules whose atoms are not linked together to form a ring
(e.g.. alkanes. alkenes. and alkynes)
compounds containing the —C0N'R2 functional group
amine compounds containing one or more organic groups bonded to an N
atom (RN-Hz. RzNH).

amino acids molecules containing an amino (NI-lg) group and an acidic carbonyl
(-—COOl-l') group that can be linked together to form proteins
handgun the separation between valence and conduction bantb
humid-free
cit Latin for "on the same side"
cosmic rays

54!
carbonyl the C=0 functional group
carbonylic acid compounds containing the —COOH functional group
chiral Chiral molecules can be in right-handed or lefi-hancbd forms. neither
of which have a plane of symmetry.
CSO Caltech Submillimeter Telescope
cumulenes successive C=C bonds
CVD chemical vapor deposition
cycloalkanes carbon rings that have the general formula CRH,“
DIE diffuse interstellar bands
DISRF difi‘use interstellar radiation field
ERE extended red emission
endothermic reaction chemical reaction requiring energy to proceed
exothermic reaction chemical reaction that releases energy upon completion
f-f free-free
FUSE Far Ultraviolet Specu'oacopir: Explorer
fullcranocs hydrogenated fullerance (Cme. m = l. 2. . . . 60). also referred to as
polyhydrofullcranoes
functional group group of atoms [in pan of a larger molecule) that has a characteristic
chemical reactivity
firll-widm-haIf—mimum
Galactic Legacy Infrared Mid-Plane Survey Extraordinaire
hydrogenated amorphous carbon
lemmelhyleneteu'amine
Hubble Space Telescope
molecules containing only C and H
inter-planetary dust particles
infrared array camera
Infrared Astronomical Satellite
Tho-Micron Slry Survey catalogue
infrared execs
ISM interstellar medium
180 Infrared Space Observatory
molecules of different structures but with the same chemical formula
WP. Inlemarional Ultraviolet Explorer
JCMT James Clerk Maxwell Telescope
Kuiper Airborne Observatory
kcrogen sedimentary organic matter insoluble in organic solvents
 Glossary 543

ketone compounds with two organic substituents bonded to a carbonyl group

(“2C=0)
Large Magellanic Cloud
LTE local thermodynamic equilibrium
methyl CH3 Smut:
methylene CH2 WP
MIPS Multihand Imaging Hintomcter
mineral a naturally occurring element or chemical compound. usually an
inorganic substance with a crystalline structure
Mira variables pulsating stats on the asymptotic giant branch. They are also trailed
long period variables.
saturated cycle-hydrocarbons
an older name for antenna
Onsala Space Observatory
Photodetector Array Camera and Spectrometer
an older name for alkanes
photodissociation regions
compounds with an —OH group directly bonded to an aromatic ring
photolysis treatment with light
animus alternate C—C and CBC bonds
wlymrphism substances that develop difl‘ferent crystal structures according to their
environment (temperature. pressure. etc.)
polysaccharides a form of carbodydrates made up of thousands of monosaccharide
(simple sugar) units

POM polyOIymethylenes
[noteins large molecules formed from chains of amino acids
Point Source Catalog
pyrolysis treatment with heat
quenched carbonaceous composites
Raman scattering inelutic scattering of a photon with an atom or molecule where the
photon gains or loses energy. leaving the atonu'molecule in a lower or
higher state
snort-area molewles molecules that have only single hoods and cannot undergo additional
reactions
SED spectral energy distribution
SIS superconductor-insulator—supereonducter
SMC Small Magellanic Cloud
SOFIA Stratospheric Observatory for Infrared Astronomy
544 Glossary

SPIRE Spectral and Human-i1: Imaging Receiver

SST Spilur Space Tblucope
misomcn omnpwndsflmhaveatamconneand influsamoudahudifferin
3~D orientalions
Lbiol compourfls com-min; the —SH fimctional group
I'ra fl! Latin for “ms": on the om: side
VLA V61 Lime Amy
VLT Very Law: New:
X-ray absorption nan-edge summit
YSO young sIcIIu' objects
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Index

2115 A feature. 343. 366 at Lyr. 55

21 micron feature. 371 amides. 254. 335. 393
2-element interferometer. 65 amines. 393
30 micron feature. 372 amino acids. 234. 254. 293. 300. 335. 336.
337. 393. 395
absolute magnitude. 55. 305 arrunonia(N'l-13). 6. I39. I96. 219. 265. 335.
aluorption. 21. 36 405. 413
absorption coefficient. 37. l26 amorphous carbon. 317. 373
absorption line profile. 126 amorphous silicates. 7. 330. 336. 333. 331.
aoctetion disks. 454. 495 332. 454
aoetaldehydc (CH3—CH=O). 296 amorphous state. 329. 334. 343. 373
acetamide. 335 Anglo-Australian ObaemtornyK Schmidt
acetic acid (CH3COOH). 296. 300 Telescope survey. 10
acetone (CHICOCHJ). 231. 235 angular resolution. 53. 63. 72
acrylene (C2H1). 139. 196. 259. 264. 270. ankerite. 333
277. 333 annealing. 332
activation energy. 412. 415 amnhite. 392
active galactic nuclei. 132. 365. 495 Antarctic Submillimeter Telescope and
adenine. 336 Remote Observatory. 115
adiabatic approximation. 427 antenna temperature. 60. 451
adiabatic index. 427 antiuacile. 349. 332
adiabatic shock. 464 anti-maser. 2'24
atkorption. 419 antisymmetric stretch. 257. 273
adsorption energy. 419 apcmrc synthesis. 63. 67. 72
acgirine. 332 APEX. 63
AFGL 613. 199. 262. 272. 275 apparent magnitude. 54. 305
AFGL sky survey. 449 aragonite. 337
MB. 357. 353. 372. 499. 502 aromatic. 196
air mass. 41 aromatics. 343. 331. 393
albedo. I3. 309. 319 Arp 299. 497
albile. 392 array pattern. 65. 71
alcohols. 23]. 2.34. 349. 393 array spacing. 66
aldehydes. 254. 365 ASTE. 63
aliphatics. 343. 331. 393. 394 asteroids. 319. 323. 377. 337. 339
alkanec. 343. 350. 360. 375 astronomical silicates. 330
aliens. 343. 375 asymmetric-lop rotator. 196. 224. 231
ALMA. 64. 113 asymptotic giant branch (AGE) starts. 4. 12.
MNC. 250 192. 249. 336. 377. 373. 443. 449. 479
0' Cam. 44-4 atmospheric transmission. 7. 57
Index

atomic absorption coefficient. 127. 131 calcium monoearbide (CaC). 251

average intensity. 613 Callisto. 391
Capella. 112
bacteria. 350 oarbenes. 271
Balmerjump. 88, 89. 172. 175 carbohydrates. 255. 300
Balmer limit. 172 carbonaceous chondi-ites. 391. 393. 394
bandgap. 342 carbonates. 337
band oscillator strength. 403 carbon chains. 270. 348. 368
Barnard 68. 310 carbon monoxide (CO). 189. 197. 198. 202.
baselines. 67 216. 217. 282, 292. 338, 402. 404. 406.
beam dilution. 61. 292 416. 496. 497
beam partem. 64 carbon onions. 348. 367
bending mode. 189. 204. 257. 269. 270. 271. carbon stars. 367, 378
273, 274. 275. 339 arbonyls. 349
bent chain carbene. 299 carbync, 348
benune (Cfiflé). 195. 211.272. 275. 217. 359 Case A. 146. 147. 151. 174
bipolar outflows. 486 Case B. [46. 147.151, 174
bituminous coal. 349 CCD. 53
blackbody. 31 centrifugal distortion. 202. 223, 265
blackbody radiation. 34 centrifugal distortion constant. 223
black holes. 4 CH. 205. 243. 402
Bohr formula. 78 CH“. 197, 205. 230. 401.416
Bohr Iadius. 85. 143. 152 CH]. 265
30! globules. l4 CH. ice. 338
bolometcrs, 62 Chandra Observatory. 109. 112
Boltzmann distribution. 155. 158 Chandrasekhar limit. 4. 5
Boltzmann equation. 31. 90. 103. 126. 154. chaotic silicates. 381
156 charge exchange reaction. 9
Born—Oppenheimer approximation. 192 charge transfer reactions. 399. 41 I
bound-bound transitions. 103. 127. 163 chemical cnrichman 3
bound-flee absorption. 56. 35. B7. 88 chemical evolution, 491
Bowen fluorescence. 160 chemical reaction network. 414
Bracken series. I49 chemical vapor deposition. 254. 345. 384
branching ratio. 410 chirality. 298
brightness temperature. 60. 157 chonurites. 391. 394
Blight Star Catalogue. 58 cbondrules. 391. 392. 393
brown dwarfs. 4. 229 C I. 115. 117
butadiynyl ndica] (C411). 237 C ignition. 4
131110.0(C4Hl0). 350. 394 Cu. 8.117.118
circumstellar envelopes. 440
C2. 193. 205. 384 £15. 298
C3. 204. 273, 274. 275 CLOUDY. I76
C3H. 296 CN. 205. 206. 207. 236. 404. 417
CM. 236. 238 C01”. 247. 415. 416
C5. 273 C01. 6. 257. 259. 261. 262. 335. 339
C5H2. 299 C02 ice. 338
C7H2. 299 cool. 349. 3511. 381. 382
calcitcs. 337 COBE.15.16.115.116. 305
calcium K line. 141 CO ice. 338. 420
 Index 561

collisional excitation. 291 DCN. 295

collisional escitationlde-excitation rates. [54 deformation mode. 267. 365. 385
collisional ionization. 32 degenerate bending mode. 258
collisionally excited lines. 103. 151. 164. 167. departure coefficient. 146
136 desorption. 311.419. 420. 421
collisional strengths. 152. 164 deuteratcd ammonia (NDg), 222
color—color diagram. 58. 59 deuterium, 213
color correction. 55. 56 diacetylene (C4H2). 270. 271
color excess. 305 diamondoids. 347. 348
color intha. 55. 57. 305 diamonfi. 253. 254. 327. 328. 329. 334. 344.
column density. 141. 156. 206. 285. 286. 310, 353. 367. 384
405 diatomic molecule. 196
combination bands. 259. 26] . 264. 339 diazenylium (MW). 216
combustion. 349. 378 dielectric constant. 129
Cornet Hale-Bopp. 333 dielecu-onic recombination. 97
Cornet Hailey. 388 diffraction pattern. 62. 72
comets. 191. 229. 319. 328. 333, 377. 387. diffuse clouds. 15. 184
388. 389. 391 difi‘uw galactic light. 12
Comet Swifl—‘lhnlc. 388. 391 diffuse interstellar bands. 367. 363
condensation temperature. 329 diffuse interstellar clouds. 420
conduction. 474 diffuse interstellar radiation field. 94. 185. 397.
conduction bands. 328. 342 398. 414. 415
cooling. I91. 199. 491 diffuse Lyman continuum. I78. 183
Copernicus satellite. 17. 105. 166. 208. 444 diffusion. 422
corundum. 334. 336. 394 dirnethyl ether (CH30CH3). 231. 296. 342
cosmic abundance. 5. 309 diopside. 332. 392
cosmic background radiation. 3, 7. 8. 205. 224. dipole moment. 189. 197, 208. 213. 222. 230.
291. 496. 497 252. 265. 271. 273. 282. 295
cosmic ray ionization. 247. 399. 400. 407 dissociative photoionizalion. 404
cosmic rays. 2|. 184. 407. 413 dissociative recombination. 399. 41]). 413. 416
Coulumb potential, 323 DNA. 234. 386
critical density. 155. 156. 282. 288 dolomite. 337
cross section. 127 Doppler broadening. I37. 405
cross shielding. 407 Doppler effect. 54. 74. 137. 440. 442. 454
cmde oil. 350 DR 21. 237
crystalline silicates. 330 Draine radiation field. 95
crystalline state. 329. 344. 378 drift velocity. 450
CS. 282. 417 DUSTCD. 316
C30. 63. 200. 229 dust shielding. 39B. 405
cumulene. 353 dust—to—gas ratio. 310
curve of growth. 142 dynamical broadening. 405
cyanides. 249 dynamic range. 61
cyanopolyynes. 192. 271. 348. 378
cyclic molecules. 232 Eanh's arrmsphere. 189. 227. 270. 303. 429
cycloalltartes. 350 effective recombination coefficient. 147. 151.
cyclopropenylidene (C3142). 191. B2 167
cytosine. 386 effective temperature. 36
Efl'elsberg Telescope, 63
damping constant. 129. 139 Einstein induced absorption coefficient. I25
562 Index

elastic collision. 403 extinction. 305

electric dipole. 403 extinction curve. 305. 306. 327. 37?
electric dipole transitions. 19'! extinction efficiency. 303. 310. 405. 450
electric-dipole transitions. I22. 123. 132. I43.
139. 191. 213. 216. 25‘)I fayalite. 331. 392
cleric-quadrupole transitions. 110. 151. 203 H: emission. 111
electron configuration. 30 ferrosilite. 331. 392
electron diffraction. 332. 394 filling factor. 149
electron scattering. I33. 131. 442 filler profile. 54
electron temperature. 133 61153.53.“
elemental depletion. 249. 251. 304. 371' fine structure constant. 35
Elias 1. 347 fine-structure lines. 33. 115. 155. 159. 167.
emergent flux. 26. 41 213. 244. 245. 251
emergent intensity, 39. 40 flair-c.3411. 332
emission. 21. 36 fluorescence. 133. 160. 349
emission coefficient. 36. 127. 143. I72. 117. fluorescent radiation. 203
312 flux. 24. 53. 54
emission measure. 125 focused ion beam microscopy. 388
emission nebulae. 9 fog. 303
emission plateaus. 353. 323. 499 forbidden lines. 110. 115. 151. 153. 159. 176.
endothennic reactions. 399. 415 183. 136
energy-balance method. 136 formaldehyde (H1CO). 139. 224, 254, 263.
enstatite. 33 I. 392 335. 405. 454. 455
EP Aqt'. 262 formal solution to the equation of transfer. 41
equation of continuity. 425. 456. 4?? fonnate (CH30CHO). 296
equation of hydrostatic equilibrium. 429 formic acid (HCOOH). 224. 333
equation of motion. 426. 467. 463. 469. 471. formyl ion [HCO+). 247. 249. 400. 416
413. 431 for-sterile. 331. 392
equation of state. 421. 430. 434 fractionation. 223. 279. 295
equation of statistical equilibrium. 146. 154. frame of reference. 462. 463. 464
159. I63. 166. 133. 234. 493 free-fall time. 433
equation of transfer. 36. 33. 44. 46. 93. 156. free-free absorption. 1‘19
291 free-free emission. 42. 176. 44?
equivalent width. 141 fringe displacement. 66
esters. 333. 350 fringe order. 65
rt 01311. 206 fringes. 65
ethane (Czflg). 265. 301. 343. 350. 362 fringe spacing. 65. 67
ethanol (CH3CH20H). 224. 296. 335 fullerane. 343. 363
enters. 349. 350 fullerene. 347. 363. 369
ethyl cyanide (CHJCH2CN). 342 functional groups. 350
ethylene (H;C=CHZ). 195. 343 fundamental transitions. 202
ethylene oxide (c-CZPhO). 232. 296 furan (c.3140). 234
ethyl group. 362 FUSE.17.105.151.166. 203.212
evaporation. 419. 420. 423
excitation temperature. 31. 77. 156. 232 (33213-06. 234
exit channels. 409 Galactic Center. 365
exit processes. 409 galactic cluster. 434
exothermic reactions. 400. 411. 412. 419 Galileo. 339
extended rad emission (ERE). 14. 363 Gamma filrtction. 36. 314
 Index 563

Ganymede. 391 heavy water. 296

Gaunt futor. 85. MS. 177. 178 hedenbergite. 392
geol'nen'ic isomers. 29B Heisenberg‘s uncertainty principle. 127. 136
GHIRS. 166 Helium. Bl
giant molecular clouds. l4 Henri Hertz Telescope. 63
GLIMPSE. l6 Herbig AdBe stars. 346
glycine (NH2CH2COOH). 2'11. 300. 386 Herschel. 275. 277
glycolaldehyde (CH20HCl-l0). 296. 303 Herschel Space Observatory. 62. 118. 247. 252
grain growth. 378 heterodyne mixers. 62
graphite. 253. 327. 323. 34-4. 349. 353. 334. hibonite. 336
393. 419. 420 high-latitude clouds. 15
grating lobes. 72 Hit regions. 1. 10. 12. 152.185.1114
gravitational collapse. 425. 437. 457 HMT. 385
gravitational waves. 21 homonuclear molecule. 20?
Green Bank Telesc0pe. 63 hot bends. 202. 261. 264
greenhouse gas. 270 HST. 17. 104
grey body. 3? HSTGl-IRS.111.124
grossite. 336 HST NICMOS. 322
Gmu'ian diagrams. 32 HST STIS. 105. 125. 166
guanine. 336 Hul-2. 152
Gum—Peterson efl'ect. 496 Humphrcys series. 149
Hund's case (a). 231. 240
H2. [95. I97. 207, 208. 212. 403. 404. 405. Hund's rules. 83
413. 420. 496 HUT. 105. 135
H21 crn line. 122. 156 hybridization. 195. 348
H2D+. 230 hydrazine (1421-14). 196
H20. 7. 259. 333 hydrocarbon plasma deposition. 349
H10 10:. 7. 333. 419 hydrocarbons. 254. 343. 348. 349. 382. 391.
H; 247. 264. 266. 400. 407 393. 394, 41?
Habing radiation field. 95. 404 hydrogen abstraction. 277. 399. 400. 411. 416
HAC. 349. 350. 351. 353. 369. 375. 382. 383. hydrogenation. 422
384 hydrogen-carbon chemistry. 39
halida. 249 hydrogen ejection. 400
halite. 336 hydrogen-oxygen chemisn'y. 399
Ht! line. 10.12. 13.20. 144.146. 143 hydrogut peroxide (H202). 196. 301
Md Collisions. 408. 412 hydrostatic equilibrium. 435
hare. 303 hydroxyl (0H) 8MP- 231
HCJN. 271 hyperfine n'lnsitions. I22. 215. 216. 222. 224.
t-tcsN. 211 236. 237. 238. 243. 245. 252. 295
HCI. 402
HCN. 6. 139. 204. 215. 254. 255. 159. 271.. 1C 418. 441
295. 333. 390. 417 ices. 33a
HO. 213. 496 ideal gas. 429
HD 44179 (the Red Rectangle). 205. 201. 358. ideal gas law. 426
368 imaging. 53
HD 73882. 212 imesrones. 337
HD 91048. 343' imidazole (C3H4N2). 234
HDO. 29 impact parameter. 400
hearing and cooling. 8. 132. 311. 427 index ofrefraction. 129. 135. 303
564 Index

inelastic collision. 408 isomers. 296. 347. 393

infi-ared active. 257. 275 isomorphism. 331
infrared cirnrs. l7 [SD SWS. 120. 149. 211. 262. 267. 333. 335.
infrared excess. 319. 450 337. 341. 351. 360
infrared inactive. 264 isothermal approximation. 428
infrared luminous galaxies. 498 isothermal shock. 464
infrared stars. 317 isotopic ratio. 124
initial-final mass relationship. 506 isotopomet. 216
initial mass function. 4 isotropic radiation. 25. 29. 3O
insulator. 328 isotropic scattering. 309
integrated emission ooelficient. 1411 [DE I7. 104.105.151.l52.166.308. 366.
integrated intensity. 24. 35 441. 444
intensity. 22. 53. 61
interacting winds. 477 jadeite. 332
intercombinarion lines. 105. 123 James Webb Space Telescope. 62
interferometers. 53. 64 JCMT. 63. 117
intergalactic medium. 496. 504 Jeans criterion. 454
internal energy. 426 Jeans length. 439
interplanetary dust particles. 21. 357. 387. 388 Jeans mass. 439
interstellar bubbles. 410. 492 Johnson photometric system. 54
interstellar extinction. 5 jump conditions. 464
interstellar reddening. l
inverse greenhouse cflect. 329 KAO, “5. 22.2. 243. 275. 357. 364
inverse P Cygni profile. 455 Keck. 341. 366
inversion transitions. 219. 222 kcrogert. 349. 352. 379. 385. 392
inward flux. 25 ltetones. 254. 333. 364. 365. 3115
ionization bounded. 175 kinetic temperature. 3 I. 77. 39. 137. 182. 285
ionization correction factors. 166 Kirchhoff‘s law, 39. 312
ion-molecule reaction. 249. 411 kosmoclrlor, 332
ion-neutral collisions. 408 Kuiper Belt. 388
IRAC. 16. 57. 62 Kuiper Belt objects. 319
LRAM. 250. 454 kutnahorite. 333
IRAS. 15. 16. 55. 56. 305. 449
IRAS 10215—5916. 332 L1 152. 215
IRAS 17150—3224. 322 L1489. 341
IRAS 21232+5050. 365 A doubling. 192. 233. 243. 251. 271
IRAS 21318+563L 313 Lamb shift. [22
MS 22272+5435. 374 Lane—Emden equation. 43]. 434
IRAS LRS. 330. 335. 336. 371 laser ablation. 332
IRAS Point Source Catalogue. 55. 56 lattice vibrations. 329
1RC+10216. 192. 250. 259. 264. 4-49 lignite. 349
1RC+10420. 240 Lil-L 230
Iron project. 164. 165 litre blanketing. 444
MS. 15. 16 line blocking. 444
ISO, 118. 150. 199. 208. 227. 230. 247, 264. line dilution, 271
267. 271. 272. 275. 277. 305. 308. 318. lipids. 255. 350
332. 335. 336. 358. 371. 502 local thermodynamic equilibrium. 33
isocyanic acid (HNCO). 224 Lorentz profile. 130. I36. 139
ISO LWS. 274 Loschtnidt number, 4")
 Index 565

L—Scoupling. 80. 104. 110, II3. 132. I92 methanol (CH30H). I99. 224. 230, 270
l-type doubling. 259. 262. 263 methyl acetylene (CHJCCH). 224
luminescence. 342 methyl (-CHJ) group. 231. 267. 298. 360. 362.
luminosity. 28 364. 365. 385
LVG approximation. 292. 293 methyl cyanide (CH3CN). 223
Lyman a. 105.143.145. 282. 318. 4-01 methylene (CH2). 244
Lyman band. 2118. 212. 403 methylene (-CHZ) group. 364. 365. 385
Lyman ,8. I34 methyl for-mate (CH30CHO). 224. 300. 342
Lyman continuum. 92. 175. 176. 182. 185 micrometeorites. 394
Lyman jump. 88. 89 Mie theory. 308
Lyman limit. ID. 79. 87. 105. “5. I45. 175. migration. 420
319. 323 minerals. 329. 330. 335
Lyman series. 146 minimum redundancy array. 72
MIPS. 62
M16. 16 Mira Variables. 4-49
M17SW. 405 molecular ions. 247. 404. 4I7
M42. 116 moment of inertia. 196. 197. 213. 218. 2.24.
M82. 497. 502 225
Mach number. 463. 470. 476 monochromatic flux. 55
Magellanic Clouds. 212. 367 muenosaccharidu. 300
rnttgnesite. 338 Mon R2. 202
magnetic-dipole mitions. Ho. [15. I22. multielernent array. 70
123. 151. 213 multiple scattering. 48
magnetic field. 323. 426 multiplelzs. 82. 152
magnetic-quadrupole transitions. I23 multiplicity. 80. 193
magnitudes. 54 Murchison metem'ite. 392. 393
Martian rocks. 357 mutual shielding. 407
means. 148. 227. 23]. 238.259 MWC 349. 149. 150
massive stars. 4. 14
mass loss. 4. 444. 448. 449 N2. 6. I97. 216. 338. 404
mass spectroscopy. 349. 38-8 N2H+. 6. 247
Mauna Ken. 7 nanodiamonds. 345. 348. 371. 384. 393. 394
Maxwell equations. 308 nanoparucles. 369. 370. 382. 384
Muwelliart distribution. 31. 90. 91. I37. 139. naphthalene (Cng). 215
153.165.172.177.408 NASA Lear Jet. 116
Me2-2. 70 natural broadening. 136
mean free path. 87. 92. I45. 182. 425 natural gas. 350
mean intensity. 29. 125.29I.403 natural width. 136
melilite (CazAIISiOT). 330 Neptune. 267
metal carbides. 251. 337. 385 neutral-neutral reaction. 412
metal hydrides. 252 neutral-neutral collision; 409
metalliciry. 5 neutrinos. 3. 21
metals. 328. 342 neutron stars. 4
metastable states. 104. 110. I72 NGC 1333. 454
meteorites. 21. 327. 328. 336. 337. 345. 357, NGC 2024. 116
377. 387. 39I NGC 6334. 223
meteors. 387' NGC 6543. 441
methane (CH..). 195. 267. 343. 350. 362. 382. NGC 7023. 360. 405
394. 418 NGC 7027. 248. 308. 357. 372. 415
Index

NGC 7533. 115. 338. 340 PACS. 62

NH. 230 PAH. 275. 348. 358. 368
NH; 300 Palomar Observatory Sky Survey. 10. S3
nicltel monochlotide (NiCl). 251 pant. 207. 219. 2.24. 225. 232. 265. 295
N 11-. 117 pal'ityJO. 104. 161
niniles. 338. 385 particle-particle aggregation. 323
N0. 204 partition function. 32. 90. 211. 234
Noheyamn Radio Observatory. 63 Paschen jump. 33. 89
none. 181. 377 Pluli exclusion principle. 80. 82. 97. 206. 3211
NRAO 12m. 35 P branch. 203
nuclear magnetic recon-nee spectroscopy. 3811 PCygni profile. 440. 441. 444
nuclear spin. 122. 123. 124. 206. 207. 215. peat. 349
216. 220. Zn. 224. 236. 2.37. 252. 295 periclasc. 336
nucleation. 373 petroleum. 347. 381
nucleosyntltesis. 3. 4. 124. 295. 491. 492. 496. Pftmd seriu. 149
497 phase function. 13.47
phenols. 349
02. 7. 197. 204. 213. 244 Phillips system. 189
03. 338 phonnns. 329
0 and B super-giants. 4. 44-0 photod'ternisu'y. 375
oblate rotator. 218 photoconduclors. 62
0 branch. 208 photodinsocintion. 193. 208. 375. 400. 401.
OCN‘. 338 404. 415. 493. 496
Odin. 213 photodissociation regions. 18. 291. 366, 405.
01-1. 402 415. 499
01-1111! stars. 59. 449 photoelectric effect. 182. 277. 323
CH maser. 449 photographic plans. 53. 61
olivines, 330 photoionizan'on. 12. 77. 79. 89. 182. 186.404.
Don Clottd. 38.8 491. 493
opacity. 1. 21. 442 photoionintion cross seclion. 164
Opacity Project. [32. 164. 165 photoluminsoence. I4. 342. 346. 368
optical constants. 129. 330 photometer. 54
optical depth. 38.145. 156. 310. 405.442. 450 photometry. 53. 54. 56
optical isomers. 29B photon dominated regions. 414. 415
orbital angular momentum quantum number. photonphete. 1
78. 30 Planck function. 31
ORFEUS. 105 plate-parallel 3mm. 36
organic tefnctory matter. 385 plane-parallel M. 25
origin of life. 396 planetary nunosphm. 213. 267
Orion. 211. 259 planetary nebulae. l. 10. 12. 151. 182. 185.
Orion Bar, 357. 360. 405.415 357. 415. 457. 479
Orion KL. 200. 229. 269 plmtetcsimnls. 396
Orion Trapezium. 330 Pleindes. 12
orlho. 207. 219. 224. 225. 232, 265. 295 PO. 2.51
onltoclue. 392 polarinbility. 408
oscillator stronmh. 5. I31. 144 polarization. 49. 323. 377
050. 237 polynoctylenic chains. 271
outward flux. 25. 36 polyncetylenic radicals. 237
overtime transitions. 202. 270 polyatomic molecules. 204. 257. 2110
 Index 567

polymerization. 423 radio recombination lines. 148. 150

polymers. 255 Raman scattering. 133. 13-4. 2.52. 254
polymorphism. 344 Raman shift. 133
polysaccharides. 300 Rayleigh criterion. 63
polyu'opic index. 431. 434 Rayleigh-Jeans approximation. 34. 60. 157.
polyy'ne. 348. 353 285. 286
POM. 385 Rayleigh scattering. I33. 252. 309
Population In stars, 134 R branch. 203
population inversion. 221. 238 R GB. 327
population synthesis. 506 recombination. 10. 32. TI. 182. 185. 491
pro-solar grains. 336. 345. 393. 394 recombination coefficient. 9l. 164
pressure broadening. 216 recombination cross section. 90.91
pie-stellar cores. 454 recombination lines. 12. 103. 142. 150. 151.
primordial molecules. I91, 496 162. 164. 167. 176.186, 295
primordial solar nebula. l9l reduced mass. 78. I96. 295
principal quantum number. 18. 80 reflection. 21
principle of detailed balance. 89. 126. 154 reticction nebulae. 12. 303. 359. 368. 414
prolate rotatot. 218. 223 refractive index. 330
propane (CJHE). 343. 350 refractory molecules. 249
proteins. :55 refractory oxides. 327. 333
proton irradiation. 386 resolving power. 65. 74
ptoton transfer reactions. 41] resonance lines. IOS. 4-40
prom-planetary nebulae. 357. 365. 324. 394 resonances. 153
prom-stars. 454 p Oph. 217
pumping mechanism. 224. 2,40 Riemann zcla function. 36. 314
purine (c—C5H4N4). 234 RNA. 234. 386
WWW {CtsHtoL 275 rocking mode. 267
pyrimidine (c—C4H4N2). 234 Rosseland mun opacity. 165
pyrolysis. 382 rotational constant. [97. 2l8. 224. 225. 25l.
pyroxencs, 330 28!
pyrrohotite. 392 r-process elements. 4. 5
pynole (C4H5N). 234 ruby. 329. 334
futile. 335. 336
Q branch. 205. 208 Rydberg constant. 78. 152
QCC. 349. 358. 365, 369. 383
quantum elec‘u'odynarnics 115. 122 8140. 405
quartz. 420 Saba equation. 32. 73. 89. 90
quasars. 495. 496 sapphire. 329. 334
S branch. 208
radiation pressure. 30. 4-42, 449 scanning electron microscopy. 382. 393
radiation recombination ooeflicient. 412 scanning transmission it-ray microscopy. 388
radiation temperature, 31. 60 scattering. 12, 46. 303
radiation tnnsfer. 227. 279. 316. 454. 493 scattcring source function. 47
rndiative association. 398. 399. 410 secondary ionization. 407
radiative cooling. 182 selection rules. 104. 143. I93. 207. 218. 222.
radiative damping. I40 227. 232. 253
radiative recombination. 400. 412 selective extinction. 1. 303
radicals. [89. 236. 251. 265. 271. 298. 362. self shielding. 39B. 405
370. 375 semi-anthracite. 349
Index

semiconductor. 323. 342. 345 stellar winds. 1. 3. 37B. 425, 440. 457. 46].
SE51". 2I7. 231. 234 492
Seyfert galaxies. 365 stereoisomer. 298
Sgt 132. 235. 274, 275 sticking coefiicienl. 420
shocks. 457. 461 stimulated emission coefficient. I25
SiC. 393. 394 stochastic. l7
side groups. 362 stochastic growth. 324
siderite. 333 stochastic heating. 321
a bond. I95 stretching mode. 257. 270. 339. 335
silicates. 317. 381. 419. 448 Striimgren radius. 93
silicon carbide (SD. 336. 371. 313, 393. Subaru 1clescope. 202
44-8 sunspots. 229
single photon excitation. 305 Sunyaev-hl'dovich effect. 497
singlet state. Bl supernovae. 3. 5. 377. 457. 492
smoke. 37B supernovae remnants. 10
snapshot. 73 Supernova remnants. I. 466
SO. 244 surface brightness. 24
$01. 199 surface migration. 42
Sobolev approximation. 292. 443. 454 Swan band. I93
sodium D line. 104 SWAS. 213. 227
SOFIA. 252. 277 symmetric su'eteh. 257
solar wind. 440 symmetric-top rotator. 196. 218. 28I
sonic point. 442 synchrotron radiation. 171
soot. 348. 349. 332
sound speed. 428. 461 Taurus dark cloud. 330
souru: function. 3!. 39. 40. 42. 44. 127 telluric opacity. 213
Soutltem Ha Sky Survey. 10 term. 82. 115
specific intensity. 22. 38 terminal velocily, 440. 442. 450
spoon-a1 energy distribution (SED). 46. 53. S6. thermal brernsstrahlung. 177
312. 313. 316. 320. 506 thermal hopping. 422
spectral index. I79 thermodynamic equilibrium. 30. 33. so
spectral resolution. 53. 73 Ihiofonnaluhyde (HZCS). 224
spectroscopic notation. 30. 192 tholins. 390
spectroscopy. 54 Thom-Kuhn sum rule. I45
spinel. 335. 336. 394 Thomson cross section. 133
spin-orbit interaction. [[5 Thomson scattering. 49. 491
spin quantum number. 78 three-body reaction. 410
SPIRE. 62 Tic. 37]. 3B4
Spitzer Spaoe Telescope. I6. 57. 62. 502 1'10. 193
spontaneous emission coefficient. [[0, 125. Titan. 390
I29 torsion. 231. 267
s-procus elements. 4. 118 total atomic absorption coefiicienl. 131
sputtering. 324. 332. 451 total flux. 35
starburst galaxies. 49B total recombination coefficient. 91. 92. 97
statistical equilibrium equation. 34. 291 trans. 29$
steady state, 34. 50, 414 transient heating. 321
Stefan—Boltzmann constant. 36 transition metals. 251
stellar atmospheres. 185 translucent clouds. 15
stellar evolution. 491 transmission electron microscopy. 348. 382
 Index 569

trimetylene (C5H1). 271 VLT. 63

Trifid Nebula (M20). I2 Voigt profile. mo
triplet state. 3] Voyager. 105. 267
Triton, 390
turbulence. 425. 435. 45‘! wagging mode, 267
No Micron Sky Survey ([RC). 449 water ['l-IZO). ”19.225. 265
two-photon radiation. I34. 172. 173. [B4 wave equation. 428
Werner band. 208
tr — 1: plane. 68. '12 white dwarfs. 4, 46!
U.S. Naval Observatory. 53 W Hya. 230. 262
UKlRT. 12]. 39l Wien's approximation. 34
ultracornpact H It regions. l2 Wien's law. 35
ultraviolet photolysis. 333, 385. 386 William Herschel Telescope. 205
Ulysses. 339 Wolf—Raye! stars. 4, 377, 440, 444
umbrella mode. 267 wollastonite. 392
uracil. 386 wustite. 335

V854 Cen. 351 XCN. 338

valence bands. 323. 342 X-ogen. 249
van det Waals force. 419 X-tay absorption near edge spectroscopy. 394
van det Waals potential. 409
V 0‘3. 337 yellow stuff. 385
very long baseline interferometry. 238 young stellar object. 44
viewing angle. 46
vinyl alcohol (CH2=CH—OH). 296 Emma temperature. IBS
vinyl cyanide (CHICHCN). J42 zero-baseline 11th. 73
vinylidene (HICC). 293 zero-magnitude flux. 54. 55. SB
virial theorem. 435. 436 zero-phonon lines. 346
visibility function. 66. 69 C 09b. 204
visual extinction. 310. 405. 40']. 4M Zodiaeal light. 338
VLA. 64, 70. 73