o Lecturer:

o Dr. Peter Gallagher

o Email:
o [email protected]

o Web:
o www.physics.tcd.ie/people/peter.gallagher/

o Office:
o 3.17A in SNIAM

PY3P05

o Section I: Single-electron Atoms

o Review of basic spectroscopy
o Hydrogen energy levels
o Fine structure
o Spin-orbit coupling
o Nuclear moments and hyperfine structure

o Section II: Multi-electron Atoms

o Central-field and Hartree approximations
o Angular momentum, LS and jj coupling
o Alkali spectra
o Helium atom
o Complex atoms

o Section III: Molecules

o Quantum mechanics of molecules
o Vibrational transitions
o Rotational transitions
o Electronic transition

PY3P05
o Lecture notes will be posted at
http://www.tcd.ie/physics/people/peter.gallagher/

o Recommended Books:
o The Physics of Atoms and Quanta: Introduction to experiement and theory
Haken & Wolf (Springer)

o Quantum Physics of Atoms, Molecules, Solids, Nuclei and Particles

Eisberg & Resnick (Wiley)

o Quantum Mechanics
McMurry

o Physical Chemistry
Atkins (OUP)

PY3P05

o Line spectra

o Emission spectra Bulb

Sun
o Absorption spectra

o Hydrogen spectrum Na

H
Emission
o Balmer Formula spectra Hg

o Bohr’s Model Cs

Chlorophyll
o Chapter 4, Eisberg & Resnick Absorption
Diethylthiacarbocyaniodid spectra

Diethylthiadicarbocyaniodid

PY3P05
o Continuous spectrum: Produced by solids, liquids & dense gases produce - no
“gaps” in wavelength of light produced:

o Emission spectrum: Produced by rarefied gases – emission only in narrow

wavelength regions:

o Absorption spectrum: Gas atoms absorb the same wavelengths as they

usually emit and results in an absorption line spectrum:

PY3P05

Gas cloud

1
2

PY3P05
o Electron transition between
energy levels result in emission
or absorption lines.

o Different elements produce

different spectra due to differing
atomic structure.

o Complexity of spectrum
increases rapidly with Z.

PY3P05

o Emission/absorption lines are due to radiative transitions:

1. Radiative (or Stimulated) absorption:

Photon with energy (E! = h" = E2 - E1) excites electron from lower energy
level.

E2 E2
E! =h"
E1 E1

Can only occur if E! = h" = E2 - E1

2. Radiative recombination/emission:
Electron makes transition to lower energy level and emits photon with energy
h"’ = E2 - E1.

PY3P05
o Radiative recombination can be either:

a) Spontaneous emission: Electron minimizes its total energy by emitting photon and
making transition from E2 to E1.

E2 E2
E!’ =h"’
E1 E1

Emitted photon has energy E!’ = h"’ = E2 - E1

b) Stimulated emission: If photon is strongly coupled with electron, cause electron to

decay to lower energy level, releasing a photon of the same energy.

E2 E2 E!’ =h"’
E! =h" E1
E1 E! =h"

Can only occur if E! = h" = E2 - E1 Also, h"’ = h"

PY3P05

o In ~1850s, hydrogen was found to emit lines at 6563, 4861 and 4340 Å.
H# H$ H!

6563 4861 4340

%& (Å)
o Lines fall closer and closer as wavelength decreases.

o Line separation converges at a particular wavelength, called the series limit.

o Balmer (1885) found that the wavelength of lines could be written

$ n2 '
" = 3646& 2 )
% n # 4(
where n is an integer >2, and RH is the Rydberg constant. Can also be written:
$1 1'
! 1/ " = R H & 2 # 2 )
%2 n (
PY3P05

!
 $1 1'
o If n =3, => 1/ " = R H & 2 # 2 ) => " = 6563 Å
%2 3 (
o Called H# - first line of Balmer series.

o ! in Balmer series:
Other lines

Name Transitions Wavelength (Å)

H# 3-2 6562.8
Highway 6563 to the US
H$ 4-2 4861.3 National Solar Observatory
5-2 4340.5
in New Mexico
H!

o Balmer Series limit occurs when n '(.

% 1 1(
1/ "# = R H ' 2 $ * => "# ~ 3646 Å
& 2 #)
PY3P05

o Other series of hydrogen:

Lyman UV nf = 1, ni)2

Balmer Visible/UV nf = 2, ni)3

Paschen IR nf = 3, ni)4
Brackett IR nf = 4, ni)5

Pfund IR nf = 5, ni)6

o Rydberg showed that all series above could be

reproduced using Series Limits
$1 1'
1/ " = R H && 2 # 2 ))
%nf ni (
o Series limit occurs when ni = !, nf = 1, 2, …

! PY3P05
o Term or Grotrian diagram for
hydrogen.

o Spectral lines can be considered as

transition between terms.

o A consequence of atomic energy levels,

is that transitions can only occur
between certain terms. Called a
selection rule. Selection rule for
hydrogen: *n = 1, 2, 3, …

PY3P05

o Simplest atomic system, consisting of single electron-proton pair.

o First model put forward by Bohr in 1913. He postulated that:

1. Electron moves in circular orbit about proton under Coulomb attraction.

2. Only possible for electron to orbits for which angular momentum is quantised,
ie., L = mvr = n! n = 1, 2, 3, …

3. Total energy (KE + V) of electron in orbit remains constant.

!
4. Quantized radiation is emitted/absorbed if an electron moves changes its orbit.

PY3P05
o Consider atom consisting of a nucleus of charge +Ze and mass M, and an electron
on charge -e and mass m. Assume M>>m so nucleus remains at fixed position in
space.

1 Ze 2 v2
o As Coulomb force is a centripetal, can write = m (1)
4 "#0 r 2 r

o As angular momentum is quantised (2nd postulate): mvr = n! n = 1, 2, 3, …

n 2!2
o Solving for v and substituting into Eqn.!1 => r = 4"#0 (2)
mZe 2
! n! 1 Ze 2
=> v = =
mr 4 "#0 n!
o The total mechanical energy is:
E = 1/2mv 2 + V
mZ 2e 4 1
" En !
=# 2 2 2 n = 1, 2, 3, … (3)
( 0)
4 $% 2! n
o Therefore, quantization of AM leads to quantisation of total energy.

! PY3P05

"13.6Z 2
o Substituting in for constants, Eqn. 3 can be written En = eV
n2
n 2 a0
and Eqn. 2 can be written r= where a0 = 0.529 Å = “Bohr radius”.
Z
!
o Eqn. 3 gives a theoretical energy level structure for hydrogen (Z=1):

o For Z = 1 and n = 1, the ground state of hydrogen is: E1 = -13.6 eV

PY3P05
o The wavelength of radiation emitted when an electron makes a transition, is (from
4th postulate): & )2 4 & )
Ei # E f 1 me 1 1
1/ " = =( + Z 2 (( 2 # 2 ++
hc ' 4 $% 0* 4 $! 3
c n
' f n i *

%1 1(
or 1/ " = R# Z 2 '' 2 $ 2 ** (4)
! & n f ni )
% 1 ( 2 me 4
where R" = ' *
& 4 #$0 ) 4 #! c
3

!
o Theoretical derivation of Rydberg formula.
!
o Essential predictions of Bohr model
are contained in Eqns. 3 and 4.

PY3P05

1. Calculate the bind energy in eV of the Hydrogen atom using Eqn 3?

o How does this compare with experiment?

2. Calculate the velocity of the electron in the ground state of Hydrogen.

o How does this compare with the speed of light?

o Is a non-relativistic model justified?

3. What is a Rydberg atom?

o Calculate the radius of a electron in an n = 300 shell.

o How does this compare with the ground state of Hydrogen?

PY3P05
o Spectroscopically measured RH does not agree exactly with theoretically derived
R!.

o But, we assumed that M>>m => nucleus fixed. In reality, electron and proton
move about common centre of mass. Must use electron’s reduced mass (µ):
mM
µ=
m+ M
o As m only appears in R!, must replace by:

! M µ
RM = R" = R"
m+ M m

o It is found spectroscopically that RM = RH to within three parts in 100,000.

!
o Therefore, different isotopes of same element have slightly different spectral lines.

PY3P05

o Consider 1H (hydrogen) and 2H (deuterium):

1
R H = R" = 109677.584 cm-1
1+ m / M H
1
RD = R"
1+ m / M D
= 109707.419 cm-1

o Using Eqn. 4, the wavelength difference is

therefore:
!
"# = # H $ #D = # H (1$ #D / # H )
= # H (1$ R H /RD )

o Called an isotope shift.

!
o H$ and D$ are separated by about 1Å.

o Intensity of D line is proportional to fraction of Balmer line of H and D

D in the sample.

PY3P05
o Bohr model works well for H and H-like atoms (e.g., 4He+, 7Li2+, 7Be3+, etc).

o Spectrum of 4He+ is almost identical to H, but just offset by a factor of four (Z2).

o For He+, Fowler found the following Z=1 Z=2 Z=3

H He+ Li2+
in stellar spectra: n n n
0 2 3 4
1 2 3
$1 1' 20 13.6 eV
1/ " = 4R He & 2 # 2 ) 2
%3 n (
40
Energy
(eV) 1
60 54.4 eV
o See Fig. 8.7 in Haken & Wolf.
! 80

100
1
120 122.5 eV

PY3P05

o Hydrogenic or hydrogen-like ions: Z=1 Z=2 Z=3

H He+ Li2+
n n n
0 2 3 4
o He+ (Z=2) 1 2 3
20 13.6 eV
o Li2+ (Z=3) Hydrogenic 2
o Be3+ (Z=4) isoelectronic 40
sequences Energy
o … (eV) 60 54.4 eV
1

80
o From Bohr model, the ionization energy is:
100
1
E1 = -13.59 Z2 eV 120 122.5 eV

o Ionization potential therefore increases rapidly with Z.

PY3P05
o We also find that the orbital radius and velocity are quantised:

n2 m Z
rn = a0 and vn = " c
Z µ n

o Bohr radius (a0) and fine structure constant (#) are fundamental constants:
!
4 "#0 ! 2 ! " =
e2
a0 = and 4 #$0 !c
me 2
!
o Constants are related by a0 =
mc"
! !
o With Rydberg constant, define gross atomic characteristics of the atom.
! energy
Rydberg RH 13.6 eV
Bohr radius a0 5.26x10-11 m
Fine structure constant ! 1/137.04

PY3P05

o Positronium
o electron (e-) and positron (e+) enter a short-lived bound state, before they annihilate each
other with the emission of two !-rays (discovered in 1949).
o Parapositronium (S=0) has a lifetime of ~1.25 x 10-10 s. Orthopositronium (S=1) has
lifetime of ~1.4 x 10-7 s.
o Energy levels proportional to reduced mass => energy levels half of hydrogen.

o Muonium:
o Replace proton in H atom with a µ meson (a “muon”).
o Bound state has a lifetime of ~2.2 x 10-6 s.
o According to Bohr’s theory (Eqn. 3), the binding energy is 13.5 eV.
o From Eqn. 4, n = 1 to n = 2 transition produces a photon of 10.15 eV.

o Antihydrogen:
o Consists of a positron bound to an antiproton - first observed in 1996 at CERN.
o Antimatter should behave like ordinary matter according to QM.
o Have not been investigated spectroscopically … yet.

PY3P05
o Bohr model was a major step toward understanding the quantum theory of the atom
- not in fact a correct description of the nature of electron orbits.

o Some of the shortcomings of the model are:

1. Fails describe why certain spectral lines are brighter than others => no
mechanism for calculating transition probabilities.

2. Violates the uncertainty principal which dictates that position and momentum
cannot be simultaneously determined.

o Bohr model gives a basic conceptual model of electrons orbits and energies. The
precise details can only be solved using the Schrödinger equation.

PY3P05

o From the Bohr model, the linear momentum of the electron is

$ Ze 2 ' n!
p = mv = m& )=
% 4 "#0 n! ( r

o However, know from Hiesenberg Uncertainty Principle, that

! ! !
"p ~ ~
"x r
o Comparing the two Eqns. above => p ~ n*p

o !
This shows that the magnitude of p is undefined except when n is large.

o Bohr model only valid when we approach the classical limit at large n.

o Must therefore use full quantum mechanical treatment to model electron in H atom.

PY3P05
o Transitions actually depend on more than a
single quantum number (i.e., more than n).

o Quantum mechanics leads to introduction on

four quntum numbers.

o Principal quantum number: n

o Azimuthal quantum number: l

o Magnetic quantum number: ml

o Spin quantum number: s

o Selection rules must also be modified.

PY3P05

Energy scale Energy (eV) Effects

Gross structure 1-10 electron-nuclear
attraction
Electron kinetic energy
Electron-electron
repulsion
Fine structure 0.001 - 0.01 Spin-orbit interaction
Relativistic corrections
Hyperfine structure 10-6 - 10-5 Nuclear interactions

PY3P05