Introduction to optical

spectroscopy
Chemistry 243

Fundamentals of
electromagnetic radiation

EE hh
h Planck's constant 6.626 1034 J s
=frequency in Hz (s-1)

c
c speed of light 3.00 108 m
s
=wavelength
1
cm 1 wavenumbers E

Electromagnetic spectrum

High
Energy

Low
Energy

http://www.yorku.ca/eye/spectrum.gif

Terminology

Spectroscopy is the study of the interaction of

light and matter

Spectrometry is the establishment of the

pattern of interaction (as a function of energy) of
light with particular forms of matter

NMR or X-Ray spectroscopy; spectroscopist

Mass spectrometry (MS); spectrometrist

Spectrophotometry is the quantitative study of

the interaction of light with matter

UV-Visible spectrophotometry

(Ive never heard anyone called a spectrophotometrist)

What chemical and/or material

properties can we measure using
spectral methods?

Broad and powerful applications

Elemental composition (often metals; CHNO)
Identity of a pure substance (what is it?)
Components of a mixture (purity?)
Amount of a substance in a mixture (how much?)
Bulk/major component, minor component,
trace component, ultra-trace component
Surface composition
Material property (stress/strain, polymer crosslinking, change of state, temperature)
Reaction rate, mechanism, products

What properties of incident or

generated light can we measure?

Absorption
Fluorescence (fast) & Phosphorescence (slow)
Thermal Emission
Chemiluminescence
Scattering
Refraction or Refractive Index
Polarization, Phase
Interference/Diffraction
Coherence
Chemistry consequent to the above

What atomic/molecular properties

affect or are affected by light?
Rotation

(typically refers to a molecule)

Vibration (typically refers to a molecule)
Electronic Excitation (atomic or molecular)
Ionization (loss of electron to yield a cation)
Combinations of the above:

Rotation-vibration (infrared/Raman)
Rotational, vibrational, electron excitation (UV-Vis)
Ionization with UV absorbance (strong excitation)

The properties you want to study

help to select a suitable wavelength
High Energy

Low Energy

Why wavenumber?

unit cm
c

E h
hc

hc
E hc( )

The energy difference between two wavenumbers is

the same regardless of spectral region or
Wavelength is not proportional to energy; it has a
reciprocal relation to energy, so: 1
E

The energy difference between two wavelengths (in nm

or angstroms) varies as a function of spectral region.

Selecting the right optical

method

Emission
Excitation Source
Plasma,
flame, or
chemical

Focus

Sorting of
Energy,
Space, and
Time

Detection

Chemiluminescence is emission
caused by a chemical reaction.
Fluorescence is emission
caused by excitation

Computer control enhances

and optimizes the info
extracted from each
instrument component.

Absorption
Transmission
and/or
Reflection can
also occur
Focus

Specimen

Energy,
Space, and
Time Sorting

Focus

Detection

Nearly linear light path geometry

for multi-wavelength,
simultaneous light detection

Absorbance

Light
Source

Wavelength ()

Relaxation is non-radiative;
sample warms up a bit via vibration and rotation

Fluorescence (fast) & Phosphorescence

(slow)
Light
Source

Focus

Specimen

(Laser)

May include
energy sorting

Energy,
Space, and
Time Sorting

Detection

Emission Power

Focus

Typical geometry 90,

but angle variable

Radiative

Raman Scattering
Light
Source

Focus

Specimen

Laser

Focus

Typical geometry 90,

but angle variable

Energy,
Space, and
Time Sorting

Detection

Same geometrical layout as fluorescence and phosphorescence,

But what happens is not the same as absorption or emission

Raman Scattering

Elastic scattering: Eex = Eout

Inelastic scattering: Ein < Eout and Ein > Eout

Eexcitation

virtual state
virtual state

-E

Eex

+E

Different classes of optical

spectroscopy
Emission

Absorbance
(UV/Vis or IR)

Lamps, LEDs

Flame,
plasma,
chemistry

Raman scattering
Fluorescence/
Phosphoresence
Lamps, LEDs,
lasers

lasers

Classes of light sources

Light sources:
Common examples

Blackbody radiation
Light emitting diode (LEDs)
Arc lamp/hollow cathode lamp
Lasers

Solid-state
Gas/excimer
Dye laser

Thermal excitation
Combinations (laser to vaporize
sample leading to thermal emission)

Continuum spectra and

blackbody radiation
A

solid is heated to incandescence

It emits thermal blackbody radiation in a continuum
of wavelengths
High E = Low = High T

blackbody
peak

Wiens
Law

b is Weins displacement constant

2.898 106 K nm
peak
T
2.898 106 K nm
roomtemp
9.82 m
295 K

human
Skoog, Fig. 6-22

2.898 106 K nm

9.35 m
310 K

Continuum spectra and

blackbody radiation

T 1200 C
T 1473 K

http://en.wikipedia.org/wiki/Image:Blackbody-lg.png
http://en.wikipedia.org/wiki/Black_body

Continuum sources

Common sources
Deuterium lamp (common Ultraviolet source)
Ar, Xe, or Hg lamps (UV-vis)
Not always continuous; spectral structure possible

http://www1.union.edu/newmanj/lasers/Light%20Production/LampSpectra.gif
http://creativelightingllc.info/450px-Deuterium_lamp_1.png

Light emitting diodes (LEDs)

First practical visible region LED

invented by Nick Holonyak in
1962 (GE; UIUC since 1963)

Father of the light-emitting-diode

An LED is a semiconductor
which emits electroluminescence

http://en.wikipedia.org/wiki/Nick_Holonyak
http://upload.wikimedia.org/wikipedia/commons/7/7c/PnJunction-LED-E.PNG
http://www.pti-nj.com/images/TimeMasterLED/LED-spectra_remade.gif

Light emitting diodes (LEDs)

Cheap, low energy, long-lasting, small, fast

Commonly used in display screens, stoplights,
circuit boards as state indicators
Lots of colors
Infrared LEDs used in remote controls

http://en.wikipedia.org/wiki/File:Verschiedene_LEDs.jpg

Line (emission) sources

Continuous

wave

Hollow cathode discharge lamp

Microwave discharge
Flames and argon plasmas

Pulsed

Pulsed hollow cathode

Spark discharge

All

these are non-laser

A line source is a light source

that emits at a narrow wavelength
called an emission line

Lasers

Light Amplification by
Stimulated Emission
of Radiation
Intense light source
Narrow bandwidth (small range < 0.01 nm)
Coherent light (in phase)

Lasers

Light Amplification by
Stimulated Emission
of Radiation

Pumping
Spontaneous Emission
Stimulated Emission
Population Inversion

Laser design

A photon
cascade!

Skoog, Fig. 7-4

Lasing medium is often:

a crystal, like ruby
a dye solution
a gas or plasma

Pumping

Generation of excited electronic states by thermal,

optical, or chemical means.

Skoog, Fig. 7-5

Spontaneous emission or
relaxation

Random in time
No directionality
Monochromatic (same ), but incoherent (not in phase)
Solid vs. dashed line 2 different photons

Skoog, Fig. 7-5

Stimulated emission

The excited state is struck by photons of precisely

the same energy causing immediate relaxation
Emission is COHERENT

Emitted photons travel in same direction

Emitted photons are precisely in phase

Skoog, Fig. 7-5

Population inversion

When the population

of excited state
species is greater
than ground state,
an incoming photon
will lead to more
stimulated emission
instead of
absorption.

Normal population
distribution

Pexcited < Pground

Inverted population

Pexcited > Pground

Skoog, Fig. 7-6

3- and 4-state lasers

Population inversion easier in 4-state system

Things stack
up here.
Population
inversion easily
achieved.

Population
relatively low
down here

Skoog, Fig. 7-7

Laser design

A photon
cascade!

Skoog, Fig. 7-4

Lasing medium is often:

a crystal, like ruby
a dye solution
a gas or plasma

Continuous wave
laser sources

Nd3+:Yttrium aluminum garnet (YAG: Y3Al5O12)

Solid state
1064 nm, 532 nm, 355 nm, 266 nm

The GTE Sylvania Model 605, uses a Nd-YAG laser rod set in a "double
elliptical reflector, is pumped by two 500-W incandescent lamps, and is
limited to a low order mode by an aperture in the laser cavity.

Continuous wave
laser sources

Helium-Neon (HeNe)

Gas, but emission comes from generated plasma (very excited

state atoms)
632.8 nm, 612 nm, 603 nm, and 543.5 nm; 1.15 & 3.39 m
Emission lines all the way out to 100 m

99%
reflective

99.9%
reflective

Continuous wave
laser sources

Ar+

Gas laser, but emission comes from ions

Uses lots of electrical power to generate ions

351.1 nm, 363.8 nm, 454.6 nm, 457.9 nm, 465.8 nm, 476.5 nm,
488.0 nm, 496.5 nm, 501.7 nm, 514.5 nm, 528.7 nm, 1092.3 n

Coherent Innova 90
Up to 5 W of output!
~100x my laser pointer

Other continuous wave

laser sources

Cu vapor
520 nm
HeCd
440 nm, 325 nm
Dye lasers

Pulsed lasers sources

Nd:YAG

Ti:sapphire

Solid stateoften pumped by Nd:YAG

Tunable output aroudn 800-1200 nm
Produces femtosecond pulses

Nitrogen

Solid state
Often nanosecond pulses
1064 nm, 532 nm, 355 nm

Gas
337 nm

Excimer lasers (gas mixtures; excited state is stable)

Tunable dye lasers ( is selective within limits)

Laser diodes
Band gap
energy, Eg

Resonant
Cavity emits
At 975 nm

Used in CD and DVD

players (not very strong)
Wavelengths now available
from IR to near UV regions

Skoog, Figs. 7-8 & 7-9.

Tip going forward

Keep

your variables straight

v for velocity or for frequency

Microsoft equation editor gives:

nu (1/s)
v vee (m/s)

I will use m for integer, textbook uses n

Easy to get mixed up with refractive index, n

Properties of electromagnetic
radiation
Transmission
Refraction
Reflection
Scattering
Optical

Components
Interference
Diffraction

Properties of electromagnetic
radiation
y A sin t
2
y A sin 2t
y
A

=
=
=
=
=

magnitude of the electric field at time t

ymax also called the amplitude of y
frequency in s -1 (cycles per second)
phase angle (an offset relative to a reference sine wave)
angular velocity in radians/sec (a handy definition)

Recall: radians = 180 degrees

Interference magnitudes add or subtract

A+B
B is in phase with A

Interference magnitudes add or subtract

A
B

A+B

B is 180 degrees ( radians) shifted from A

Interference magnitudes add or subtract

A
B

A+B

B is 90 degrees ( / 2 radians) shifted from A

Interference between waves of

different frequency

Wave 1 + 2

1 2
Skoog, Fig. 6-5

Transmission through
materials

Compared to vacuum, the velocity of light is reduced

when propagating through materials that have
polarizable electrons.

Wavelength also decreases

All electrons are polarizable to some extent

c
ni
vi

Skoog, Fig 6-2.

E h
constant
c medium
cvacuum = 2.99792 x 108 m s-1

Index of Refraction

Refractive index is measure of how much light is slowed:

c
ni vacuum refractive index at a given wavelength ( 1)
vi

vi velocity at a given wavelength

Refractive index is wavelength- and temperaturedependent for many materials:

Material

n @ 589.3 nm

Vacuum (air)

1.00

Water

1.33

Hexadecane

1.43

Quartz

1.46

Toluene

1.49

Glass

1.58

Wavelength-dependence of nSiO2

(light flint)

http://www.rp-photonics.com/refractive_index.html

Refraction
Snells

law:

sin 1 n2 v1

sin 2 n1 v2
immersion lenses
for high magnification
microscopy

Medium 1
Medium 2

Oil

Here, n2 > n1
Velocities, not frequencies

Skoog, Fig. 6-10

For your information

Book

Error on page 141, equation 6-12:

sin 1 n2 v1 velocity in medium 1

sin 2 n1 v2 velocity in medium 2

This is correct: Snells Law of Refraction

Reflection

Amount of loss at a reflection increases with refractive

index mismatch.

For right angle light entrance into a medium:

I r n2 n1
reflected intensity

1
2
incident intensity
I 0 n2 n1
2

Reflective loss is angle-dependent

Fresnel equations (which we will skip)

Most important case is: total internal reflection

Total internal reflection

Light incident upon a material

of lesser refractive index is
bent away from the normal so
that the exit angle is greater
than then incident angle.

nentry > nexit

2

At the critical incident angle,

the exit angle is 90 - beam
does not exit
Angles larger than the critical
incident angle lead to total
internal refection (TIR)

> 1

Medium2
Medium1

nexit
nentry

n1 sin 1 n2 sin 2
nentry sin 1 nexit sin 2
nentry sin critical nexit sin( 90)
nentry sin critical nexit

Modified from Skoog

When this is true, 1 = critical entry angle for TIR

Total internal reflection

nentry sin critical nexit
When this is true,
1 = critical entry angle for TIR.
If 1 > critical result is TIR.

TIR fluorescence
microscopy:

Evanescent wave samples a very

narrow slice of the sample very near
to the dielectric interface
Typically ~200 nm
http://hyperphysics.phy-astr.gsu.edu/Hbase/phyopt/totint.html
http://www.olympusmicro.com/primer/techniques/fluorescence/tirf/tirfintro.html

Total internal reflection

nentry sin critical nexit
When this is true,
1 = critical entry angle for TIR.
If 1 > critical result is TIR.

TIR fluorescence
microscopy:

Good for studying adhered cells; low background

http://hyperphysics.phy-astr.gsu.edu/Hbase/phyopt/totint.html
http://www.olympusmicro.com/primer/techniques/fluorescence/tirf/tirfintro.html

Fiber optics

Extruded strands of glass

or plastic that guide light
via total internal reflection.

Core has higher refractive

index than cladding.
Flexible
Material choice allows
transmission in UV, visible,
or IR

Skoog, Fig 7-39.

Follows all the rules of

Snells Law

Scattering
Raman

scattering

Inelastic scattering

offset from by frequency of molecular vibrations

Rayleigh

Molecules or aggregates smaller than

Intensity ~ 1/4

Mie

scattering

scattering

Particles large (or comparable) to

Used for particle sizing

Essential optical elements

Lenses
Mirrors
Prisms
Filters
Gratings

Basic optical components

Mirrors

Reflection

Concave mirror is
converging

Prisms

Refraction

n1 sin 1 n2 sin 2

Snells Law

Filters

Absorption filters

Cheap, visible region;

colored glass
Cutoff filters
long-pass
short-pass

Interference filters

2d
m
cos
air n
2dn
air
m cos
mm=
integer
interger

d = thickness of dielectric layer

n = refractive index of dielectric medium

is usually zero
so, cos = 1.
Also, m is usually 1

= wavelength in the dielectric material

Skoog, Fig. 7-12

Interference filters

Almost
monochromatic

Bandwidth of a filter is
width at half-height
(aka full-width @ half-max)

Skoog, Fig. 7-13

Diffraction of coherent radiation:

Interference at work

Consequence of
interference

d = distance from slit B to C

m d sin

constructive

m integer

constructive

destructive
destructive

(m is the order of interference)

constructive

Distance x to y is one

m is:
0 for E
1 for D

Skoog, Figs. 6-7, 6-8

m used here, text uses n

Diffraction of coherent radiation:

Interference at work

Consequence of
interference

m d sin
m integer

(m is the order of interference)

m d sin
BC DE

OD
m used here, text uses n

Skoog, Fig. 6-8

You can now determine the

wavelength of light
based on things that
are easy to measure!

Monochromators
Used

to spatially separate different

wavelengths of light: prisms, gratings

Bunsen prism monochromator

Czerny-Turner grating monochromator

Skoog, Fig. 7-18

Gratings and monochromators

Reflection + diffraction: echellette-type grating

m CB BD

CB d sin i
BD d sin r
m d sin i sin r
The condition for
constructive interference.
The m = 1 line is most intense.

Skoog, Fig. 7-21

The surface contains grooves or blazes.

Take a look at
Example 7-1,
Page 184.

Monochromators
Used

to spatially separate different

wavelengths of light: prisms, gratings

Czerny-Turner grating monochromator

Skoog, Fig. 7-18

Useful metrics for

monochromators

Dispersion (page 185); high dispersion is good

Integration of m d sin i sin r at constant i gives the
angular dispersion:

dr
m

d d cos r

r = angle of reflection
d = distance between blazes

Linear dispersion, D, is the variation of along the

focal plane position, y: D dy f dr
A measure of
d
d
f focal length

Reciprocal linear dispersion, D-1:

D 1

d d cos r
d

for small r
dy
mf
mf

the ability to
separate wavelengths

More useful, results in

D-1 in nm per mm
or similar

Useful metrics for

monochromatorscontinued
Resolving

power (R; unitless)

Limit of monochromators ability to distinguish

between adjacent wavelengths.

mN (unitless)

N Number of grating blazes illuminate d

Light

gathering power (f-number, F; unitless)

Collection efficiencyimprove for maximizing S/N

Efficiency scales as the inverse square of F

F f d
f focal length of collimating mirror or lens
d diameter of collimating optic

d
f

Complications with
monochromators
Overlap

of orders

m = 1, = 600 nm and
m = 2, = 300 nm spatially overlap

You can get s mixed up if light source contains many

wavelengths

Additional

wavelength selection often needed

Filter, prism, detector selection device, digital

analysis after data collection, background
subtraction
Might need to use a different light source if your
wavelength of interest is not clean

Slit width and spectral

resolution of a spectrometer

Tradeoff exists between sensitivity and resolution

High intensity = high sensitivity (low noise)

Two basic concepts:

If you make the entrance slit width too big, you let in a lot of
light (thats good high intensity), but it can be multiwavelength; a large section of light dispersed in is let in

If you make the entrance slit width too small, you let in less
light (less intensity), but its range is smaller

Poor light intensity, good spectral resolution

Entrance slit (creates image) and exit slit (output filter)

Good light intensity, poor spectral resolution

Usually the same width

Optimal slit width based upon grating dispersion

Slit width

For just passing 2

Skoog, Fig. 7-24

Slit width

Both entrance
and exit slits
narrowed
from top to
bottom

Ptotal

w is slit width
If spectral bandwidth
is /2, good
spectral resolution

Skoog, Fig. 7-25

Slit width

Watch the effect of adjusting the slit width and the

resultant spectral bandwidth on the following data sets of
benzene vapor.
w is slit
width

Skoog, Fig. 7-26

Optical Photodetectors
More sensitive

Less sensitive

A.
B.
C.
D.
E.
F.
G.
H.
I.

Photomultiplier tube (PMT)

CdS photoconductivity
GaAs photovoltaic cell
CdSe photoconductivity cell
Se/SeO photovoltaic cell
Si photodiode
PbS photoconducitivity
Thermocouple
Golay cell
These generally make current
or voltage when light hits them.

Ideal photodetector
(photon transducer)
High

sensitivity
High S/N
Fast response time
Signal directly
proportional to # of
photons detected
Zero dark current

The blank is zero

S
Photons counted
N
Or, equivalently,

S kP

Ideal photodetector
(photon transducer)
High

sensitivity
High S/N
Fast response time
Signal directly
proportional to # of
photons detected
Zero dark current

y
t
i
l
s
a
e
e
R rud
t
In

The blank is zero

S kP
Heres what really happens:

S kP kdark
Signal is
Function of

Constant dark
current term
(non-zero)

Three main
photodetector types
Photon

Photomultiplier tubes (PMTs)

Charge

transducers (directly count photons)

transfer devices

Charge injection devices (CID)

Charge coupled devices (CCD)

Thermal

transducers

Photons strike the transducer

Temp increases
Temp increase increases conductivity

Current or voltage are measured

Vacuum phototube

Cathode is coated with

photo-emissive material
Emitted electrons are
collected anode.
# of electrons is directly
proportional to # of photons.
Current is easy to amplify.
Usually have small dark
current.
Operate at ~ 90V bias
Not so portable
Skoog, Fig. 7-29.

Photomultiplier tube (PMT)

# of electrons is amplified
by photoelectric effect
upon acceleration
towards dynodes

Each dynode biased ~ 90V

more positive than previous
dynode (or cathode)

Voltage drop accelerates

electrons to dynode
cascade
Amplification: 106-107
electrons per incident
photon; electron cascade
http://www.nt.ntnu.no/users/floban/KJ%20%203055/PMT.jpg

Photomultiplier tube (PMT)

Advantages:
Very sensitive in UV-Vis region,
single photon sensitivity
Cooled PMT has very low
background
(k
dark approaches zero)
Linear response
Fast response
Disadvantages
Easily damaged by intense (ambient)
light
Noise is power dependent
Single channel: cant use for imaging

Photovoltaic cell

Light strikes a
semiconductor (Se) and
generates electrons and
holes
Magnitude of current is
proportional to # of
photons
Requires no external
power supply!
Disadvantages: hard to
amplify signal and fatigue
(wears out)
Useful for portable
analyses, field work,
outdoor setting

Skoog, Fig. 7-28

Photodiodes
(Silicon 190-1100 nm, InGaAs 900 1600 nm)

Reverse-biased p-n junction

Conductance goes to near

zero

Photons create electron hole

pairs that migrate to opposite
contacts and generate
current
Battery powered

Portable applications
Are not as prone to some
electronic noise sources

60 Hz line noise

Skoog, Fig. 7-32

Multichannel transducers
Allow

simultaneous interrogation of multiple

wavelengths
Imaging
Photodiode arrays (1-D array)
Charge-transfer devices (2-D array)

Charge-injection devices
Charge-coupled device (CCD)
CMOS

Photodiode arrays

Each diode has defined

spatial address
Advantages

Disadvantages

Multichannel (used for

imaging)
More robust than PMT
Not as sensitive as PMT
Slower response time

Common in cheaper UV-Vis

instruments

Often perfectly adequate

Skoog, Fig. 7-33

Charge transfer devices

Converts light into charge

Negative-biasing leads to
increased capture of holes
under pixel electrodes

Photon ejects electron and

the device collects and stores
charges

Potential well

105-106 charges per pixel

Configured as CID or CCD

Schematic is for CID
Skoog, Fig. 7-35

Charge transfer devices

(continued)

Charge-injection device (CID)-measures

accumulated voltage change (nondestructive
read; persistent after read)

Charge-coupled device (CCD)-moves

accumulated charges to amplifier and readout
(destructive read; gone after read)

Measurements can be made while integrating

Very high sensitivity; 104-105 pixels

High resolution spectral imaging

Complementary metal oxide semiconductor

(CMOS)

Webcam technology: CHEAP!

OK sensitivity, large pixel density

CCD (charge coupled device)

Pixels

read one at a time by sequential

transfer of accumulated charge

From: CCD vs. CMOS: Facts and Fiction by Dave Litwiller, in Photonics Spectra, January 2001

CMOS detectors
Digital

camera and webcam technology

Each pixel can be read individually

Image from Wikipedia

From: CCD vs. CMOS: Facts and Fiction by Dave Litwiller, in Photonics Spectra, January 2001

CCD

Essentially serial
Each pixel read one at a
time by common external
circuitry

CMOS

Voltage conversion and

buffering

Outputs an analog signal

Historically gave higherresolution images
Relatively expensive

Essentially parallel
Each pixel has its own red
out circuitry on-chip

Outputs a digital signal

Reduced area for light
absorption
Relatively inexpensive

High power consumption

Up to 100x more than

CMOS

Allows amplification and

noise correction
More susceptible to noise

Highly commercialized fab

Runs on less power

Requires less off-chip

circuitry

Both approaches exist today

Photoconductivity transducers
Semiconductors

whose resistance decreases

when they absorb light
Absorption promotes electron to conduction
band.
Useful in near IR( = 0.75 to 3 m)
Cooling allows extension to longer
wavelengths by reducing thermal noise

Thermal transducers

Solution for IR region (low energy photons)

Thermocouples

Bolometer (thermistor)

Light absorbed heats the junction (two pieces of dissimilar

metal) which leads to a change in voltage relative to a
reference thermocouple.
Material changes resistance as a function of temp

Pyroelectric devices

Temperature-dependent capacitor
Change in temperature leads to change in circuit current