SKA6014

ADVANCED ANALYTICAL CHEMISTRY

TOPIC 5
Rotational and Vibrational Spectroscopy

Azlan Kamari, PhD
Department of Chemistry
Faculty of Science and Mathematics
Universiti Pendidikan Sultan Idris
Vibrational and Rotational Spectroscopy
Core techniques:

Infrared (IR) spectroscopy

Raman spectroscopy

Microwave spectroscopy


The Electromagnetic Spectrum
The basic!
Microwave
Infrared (IR)
The History of Infrared and Raman Spectroscopy
Infrared (IR) Spectroscopy:
First real IR spectra measured by Abney and Festing in 1880s
Technique made into a routine analytical method between 1903-
1940 (especially by Coblentz at the US NBS)
IR spectroscopy through most of the 20
th
century is done with
dispersive (grating) instruments, i.e. monochromators
Fourier Transform (FT) IR instruments become common in the
1980s, led to a great increase in sensitivity and resolution
Raman Spectroscopy:
In 1928, C. V. Raman discovers that small changes occur the
frequency of a small portion of the light scattered by molecules.
The changes reflect the vibrational properties of the molecule
In the 1970s, lasers made Raman much more practical. Near-IR
lasers (1990s) allowed for avoidance of fluorescence in many
samples.
Infrared Spectral Regions
IR regions are traditionally sub-divided as follows:
Region Wavelength
(), m
Wavenumber
(v), cm
-1

Frequency
(v), Hz
Near 0.78 to 2.5 12800 to 4000 3.8 x 10
14

to
1.2 x 10
14

Mid 2.5 to 50 4000 to 200 1.2 x 10
14

to
6.0 x 10
12


Far 50 to 1000 200 to 10 6.0 x 10
12

to
3.0 x 10
11


After Table 16-1 of Skoog, et al. (Chapter 16)
What is a Wavenumber?
Wavenumbers (denoted cm
-1
) are a measure of frequency
For an easy way to remember, think waves per centimeter

Relationship of wavenumbers to the usual frequency and
wavelength scales:
Image from www.asu.edu

v
10000
1
=

cm
Converting
wavelength () to
wavenumbers:
Rotational and Vibrational Spectroscopy: Theory
Overview:
Separation of vibrational and rotational contributions to
energy is commonplace and is acceptable
Separation of electronic and rovibrational interactions

Basic theoretical approaches:
Harmonic oscillator for vibration
Rigid rotor for rotation

Terminology:
Reduced mass (a.k.a. effective mass):
2 1
2 1
m m
m m
+
=
Rotational Spectroscopy: Theory
Rotational energy levels can be
described as follows:
D J B J J
3
) 1 ( ) 1 ( ) ( + + = v
c r h B
2
0
2
8 / t =
2 3
/ 4
c
B D e =
Where:
c is the speed of light
k is the Hookes law force constant
r
0
is the vibrationally-averaged bond length
The rotational constant:
The centrifugal distortion coefficient:
u
k
c
c
t
e
2
1
=
Example for HCl:
B
0
= 10.4398 cm
-1

D
0
= 0.0005319 cm
-1

r
0
= 1.2887

is the reduced mass
h is Plancks constant
e
0
= 2990.946 cm
-1
(from IR)
k = 5.12436 x 10
5
dyne/cm
-1

For J = 0, 1, 2, 3
Vibrational Spectroscopy: Theory
Harmonic oscillator based on the classical spring
( )
m
h v E v
2
1
+ =
v
m
is the natural frequency of the oscillator (a.k.a. the fundamental vibrational wavenumber)
k is the Hookes law force constant (now for the chemical bond)
u
k
m
t
v
2
1
=
v is the vibrational quantum number
h is Plancks constant
Since v must be a whole number.
The potential energy function is:
2
2
1
) ( ) (
e HO
r r k r E =
Note all E are
potential energies (V)!
or
2 2
2
1
) ( ) 2 ( ) (
e m HO
r r c r E = v t
t
v
k h
h E
m
2
= = A

v
k
12
10 3 . 5

= and
r is the distance (bond distance)
r
e
is the equilibrium distance
Vibrational Spectroscopy: Theory
Potential energy of a harmonic oscillator:
Anharmonic Corrections
Anharmonic motion: when the restoring force is not
proportional to the displacement.
More accurately given by the Morse potential function
than by the harmonic oscillator equation.
Primarily caused by Coulombic (electrostatic)
repulsion as atoms approach




Effects: at higher quantum numbers, AE gets smaller, and the (Av =
+/-1) selection rule can be broken
Double (Av = +/-2), triple (Av = +/-3), and higher order transitions
can occur, leading to overtone bands at higher frequencies (NIR)
2 ) (
) 1 ( ) (
e
r r a
e Morse
e hcD r E

=
D
e
is the dissociation energy
e
m
hcD
c
a
2
) 2 (
2
v t
=
Vibrational Coupling
Vibrations in a molecule may couple changing each
others frequency.
In stretching vibrations, the strongest coupling occurs
between vibrational groups sharing an atom
In bending vibrations, the strongest coupling occurs
between groups sharing a common bond
Coupling between stretching and bending modes can occur
when the stretching bond is part of the bending atom
sequence.
Interactions are strongest when the vibrations have similar
frequencies (energies)
Strong coupling can only occur between vibrations with the
same symmetry (i.e. between two carbonyl vibrations)

Vibrational Modes and IR Absorption
Number of modes:
Linear: 3n 5 modes
Non-linear: 3n 6 modes

Types of vibrations:
Stretching
Bending

Examples:
CO
2
has 3 x 3 5 = 4
normal modes

Symmetric
No change in dipole
IR-inactive
Asymmetric
Change in dipole
IR-active
Scissoring
Change in dipole
IR-active
IR-active modes require dipole changes during rotations and
vibrations!
Vibrational Modes: Examples
IR-activity
requires dipole
changes during
vibrations!



Inactive
Active
Active
Active
Inactive
Inactive
Active
IR Spectra: Formaldehyde
Certain types of vibrations have distinct IR frequencies
hence the chemical usefulness of the spectra
The gas-phase IR spectrum of formaldehyde:
Formaldehyde spectrum from: http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/InfraRed/infrared.htm#ir2
Results generated using B3LYP//6-31G(d) in Gaussian 03W.
Tables and simulation results can help assign the vibrations!
(wavenumbers, cm
-1
)
Rayleigh and Raman Scattering
Only objects whose dimension is ~1-1.5 will scatter EM
radiation.

Rayleigh scattering:
occurs when incident EM radiation induces an oscillating dipole in
a molecule, which is re-radiated at the same frequency
Raman scattering:
occurs when monochromatic light is scattered by a molecule, and
the scattered light has been weakly modulated by the
characteristic frequencies of the molecule

Raman spectroscopy measures the difference between
the wavelengths of the incident radiation and the
scattered radiation.

The Raman Effect
Polarization changes are
necessary to form the
virtual state and hence
the Raman effect

This figure depicts
normal (spontaneous)
Raman effects
hv
1

Scattering timescale ~10
-14
sec
(fluorescence ~10
-8
sec)
Virtual state
Virtual state
hv
1

Ground state
(vibrational)
The incident radiation excites virtual states (distorted
or polarized states) that persist for the short timescale
of the scattering process.
Excited state
(vibrational)
hv
1
hv
2

Stokes line
hv
1
hv
2

Anti-Stokes line
More on Raman Processes
The Raman process: inelastic scattering of a photon when it is
incident on the electrons in a molecule
When inelastically-scattered, the photon loses some of its
energy to the molecule (Stokes process). It can then be
experimentally detected as a lower-energy scattered
photon
The photon can also gain energy from the molecule (anti-
Stokes process)

Raman selection rules are based on the polarizability of the
molecule

Polarizability: the deformability of a bond or a molecule in
response to an applied electric field. Closely related to the
concept of hardness in acid/base chemistry.
P. W. Atkins and R. S. Friedman, Molecular Quantum Mechanics, 3
rd
Ed. Oxford: 1997.
More on Raman Processes
Consider the time variation of the dipole moment induced by incident
radiation (an EM field):
) ( ) ( ) ( t t t c o =
P. W. Atkins and R. S. Friedman, Molecular Quantum Mechanics, 3
rd
Ed. Oxford: 1997.
EM field Induced dipole moment
Expanding this product yields:
( ) t t t t ) cos( ) cos( cos ) (
int int 0
4
1
0
e e e e oc e oc + + A + =
Rayleigh line
Anti-Stokes line Stokes line
polarizability
If the incident radiation has frequency e and the polarizability of the
molecule changes between o
min
and o
max
at a frequency e
int
as a result
of this rotation/vibration:
( ) t t t e c e o o cos cos ) (
0 int
2
1
A + =
mean polarizability Ao = o
max
- o
min
The Raman Spectrum of CCl
4

Figure is redrawn from D. P. Strommen and K. Nakamoto, Amer. Lab., 1981, 43 (10), 72.
Observed in
typical
Raman
experiments
v
0
= 20492 cm
-1

0
= 488.0 nm
Anti-Stokes lines
(inelastic scattering)
-218
Raman shift cm
-1

v
0
= (v
s
-
0
)
-200
Stokes lines
(inelastic scattering)
-400 400 200
218
314
-314
-459
459
0
Rayleigh line
(elastic scattering)
Raman-Active Vibrational Modes
Modes that are more polarizable are more Raman-active

Examples:
N
2
(dinitrogen) symmetric stretch
cause no change in dipole (IR-inactive)
cause a change in the polarizability of the bond as the bond
gets longer it is more easily deformed (Raman-active)
CO
2
asymmetric stretch
cause a change in dipole (IR-active)
Polarizability change of one C=O bond lengthening is
cancelled by the shortening of the other no net polarizability
(Raman-inactive)

Some modes may be both IR and Raman-active, others
may be one or the other!
The Raman Depolarization Ratio
Raman spectra are excited by linearly polarized radiation
(laser).
The scattered radiation is polarized differently depending
on the active vibration.
Using a polarizer to capture the two components leads to
the depolarization ratio p:
=

=
I
I
p
The depolarization ratio p can be useful in interpreting the
actual vibration responsible for a Raman signal.
Instrumentation for Vibrational Spectroscopy
Absorption vs. Emission for IR spectroscopy:
Emission is seldom used for chemical analysis
The sample must be heated to a temperature much greater than its
surroundings (destroying molecules)
IR emission is widely used in astronomy and in space applications.
Two IR Absorption methods:
Dispersive methods: Scanning of wavelengths using a grating (common
examples are double-beam, like a spectrometer discussed in the optical
electronic spectroscopy lecture).


Fourier-transform methods: based on interferometry, a method of
interfering and modulating IR radiation to encode it as a function of its
frequency.
Radiation
Source
Sample
Wavelength
Selector
Detector
(transducer)
Radiation
Source
Interferometer Sample
Detector
(transducer)
Why Build Instruments for Fourier Transform Work?
Advantages:
The Jacqinot (throughput) advantage: FT instruments have
few slits, or other sources of beam attenuation
Resolution/wavelength accuracy (Connes advantage):
achieved by a colinear laser of known frequency
Fellgett (multiplex) advantage: all frequencies detected at
once, signal averaging
These advantages are critical for IR spectroscopy
The need for FT instruments is rooted in the detector
There are no transducers that can acquire time-varying signals
in the 10
12
to 10
15
Hz range they are not fast enough!
Why are FT instruments not used in UV-Vis?
The multiplex disadvantage (shot noise) adversely affects
signal averaging it is better to multiplex with array detectors
(such as the CCD in ICP-OES)
In some cases, technical challenges to building interferometers
with tiny mirror movements
Inteferometers for FT-IR and FT-Raman
The Michelson
interferometer, the
product of a famous
physics experiment:
Produces
interference
patterns from
monochromatic
and white light
Figures from Wikipedia.org
Inteferometers
For monochromatic
radiation, the
interferogram looks like
a cosine curve
For polychromatic
radiation, each
frequency is encoded
with a much slower
amplitude modulation
The relationship
between frequencies:
Example: mirror rate = 0.3 cm/s modulates 1000 cm
-1
light at 600 Hz
Example: mirror rate = 0.2 cm/s modulates 700 nm light at 5700 Hz
v
c
v
f
M
2
=
Where:
v is the frequency of the radiation
c is the speed of light in cm/s
v
m
is the mirror velocity in cm/s
The Basics of the Fourier Transform
The conversion from time- to frequency domain:
50 100 150 200 250
-1
-0.5
0.5
1
50 100 150 200 250
0.5
1
1.5
2
FT
50 100 150 200 250
-1.5
-1
-0.5
0.5
1
1.5
2
50 100 150 200 250
0.5
1
1.5
2
2.5

=
1
0
/ 2
1
N
k
N ikn
k n
e d
N
f
t
}

=
b
a
d t f t K g e e e ) ( ) , ( ) (
1
) t exp( ) , ( i t K = e Continuous:
Discrete:
FT
FTIR Spectrometer Design
Michelson
Interferometer
IR Source
Sample
Moving Mirror
Fixed Mirror
Beamsplitter
Detector
Interferogram
Fourier Transform - IR Spectrum
It is possible to build a detector that detects multiple
frequencies for some EM radiation (ex. ICP-OES with CCD,
UV-Vis DAD)
FTIR spectrometers are designed around the Michelson
interferometer, which modulates each IR individual
frequency with an additional unique frequency:
IR Sampling Methods: Absorbance Methods
Salt plates (NaCl): for liquids (a drop) and small amounts of
solids. Sample is held between two plates or is squeezed onto
a single plate.

KBr/CsI pellet: a dilute (~1%) amount of sample in the halide
matrix is pressed at >10000 psi to form a transparent disk.
Disadvantages: dilution required, can cause changes in
sample

Mulls: Solid dispersion of sample in a heavy oil (Nujol)
Disadvantages: big interferences

Cells: For liquids or dissolved samples. Includes internal
reflectance cells (CIRCLE cells)

Photoacoustic (discussed later)
IR Sampling Methods: Reflectance Methods
Specular reflection: direct
reflection off of a flat surface.
Grazing angles

Attenuated total reflection
(ATR): Beam passed through
an IR-transparent material
with a high refractive index,
causing internal reflections.
Depth is ~2 um (several
wavelengths)

Diffuse reflection (DRIFTS): a
technique that collects IR
radiation scattered off of fine
particles and powders. Used
for both surface and bulk
studies.
Figures from http://www.nuance.northwestern.edu/KeckII/ftir7.asp
ATR
DRIFTS
IR Sources
Nernst glower: a rod or cylinder made from several
grams of rare earth oxides, heated to 1200-2200K by an
electric current.

Globar: similar to the Nernst glower but made from
silicon carbide, electrically heated. Better performance at
lower frequencies.

Incandescent Wires: nichrome or rhodium, low intensity

Mercury Arc: high-pressure mercury vapor tube, electric
arc forms a plasma. Used for far-IR

Tungsten filament: used for near-IR

CO
2
Lasers (line source): high-intensity, tunable, used for
quantitation of specific analytes.
IR Detectors
Thermal transducers
Response depends upon heating effects of IR radiation
(temperature change is measured)
Slow response times, typically used for dispersive instruments
or special applications
Pyroelectric transducers
Pyroelectric: insulators (dielectrics) which retain a strong electric
polarization after removal of an electric field, while they stay
below their Curie temperature.
DTGS (deuterated triglycine sulfate): Curie point ~47C
Fast response time, useful for interferometry (FTIR)
Photoconducting transducers
Photoconductor: absorption of radiation decreases electrical
resistance. Cooled to LN
2
temperatures (77K) to reduce thermal
noise.
Mid-IR: Mercury cadmium telluride (MCT)
Near-IR: Lead sulfide (NIR)
Raman Spectrometers
The basic design dispersive Raman scattering system:

Special considerations:
Sources: lasers are generally the only source strong enough to
scatter lots of light and lead to detectable Raman scattering

Avoiding fluorescence: He-Cd (441.6 nm), Ar ion (488.0 nm,
514.5 nm), He-Ne (632.8), Diode (782 or 830), Nd/YAG (1064)

Sample
Wavelength
Selector
Detector
(photoelectric transducer)
Radiation
source
(90 angle)
Modern Raman Spectrometers
FT-Raman spectrometers also make use of Michelson
interferometers
Use IR (1 m) lasers, almost no problem with fluorescence for
organic molecules
Have many of the same advantages of FT-IR over dispersive
But, there is much debate about the role of shot noise and
whether signal averaging is really effective

CCD-Raman spectrometers dispersive spectrometers that
use a CCD detector (like the ICP-OES system described in the
Optical Electronic lecture)
Raman is detected at optical frequencies!
Generally more sensitive, used for microscopy
Usually more susceptible to fluorescence, also more complex

Detectors - GaAs photomultiplier tubes, diode arrays, in
addition to the above.
More on Raman
Raman can be used to study aqueous-phase samples
IR is normally obscured by H
2
O modes, these happen to be less
intense in Raman
However, the water can absorb the scattered Raman light and
will damp the spectrum, and lower its sensitivity

Raman has several problems:
Susceptible to fluorescence, choice of laser important
When used to analyze samples at temperatures greater than
250C, suffers from black-body radiation interference (so does
IR)
When applied to darkly-colored samples (e.g. black), the Raman
laser will heat the sample, can cause decomposition and/or
more black-body radiation
Applications of Raman Spectroscopy
Biochemistry: water is not strongly detected in Raman experiments,
so aqueous systems can be studied. Sensitive to e.g. protein
conformation.

Inorganic chemistry: also often aqueous systems. Raman also can
study lower wavenumbers without interferences.

Other unique examples:
Resonance Raman spectroscopy: strong enhancement (10
2

10
6
times) of Raman lines by using an excitation frequency close
to an electronic transition (Can detect umol or nmol of analytes).
Surface-enhanced Raman (SERS): an enhancement obtained for
samples adsorbed on colloidal metal particles.
Coherent anti-Stokes Raman (CARS): a non-linear technique
using two lasers to observe third-order Raman scattering used
for studies of gaseous systems like flames since it avoids both
fluorescence and luminescence issues.
Applications of Raman Spectroscopy
Raman in catalysis research:
Useful for the study of zeolite interiors
Fluorescence can be a problem, but one approach is to use
UV light (257 nm) which avoids it just like switching to the
IR (but at the risk of decomposition)

Raman microscopy:
offers sub-micrometer lateral resolution combined with depth-
profiling (when combined with confocal microscopy)
Comparison of IR and Raman Spectroscopy
Advantages of Raman over IR:
Avoids many interferences from solvents, cells and sample
preparation methods
Better selectivity, peaks tend to be narrow
Depolarization studies possible, enhanced effects in some cases
Can detect IR-inactive vibrational modes

Advantages of IR over Raman:
Raman can suffer from laser-induced fluorescence and
degradation
Raman lines are weaker, the Rayleigh line is also present
Raman instruments are generally more costly
Spectra are spread over many um in the IR but are compressed
into several nm (20-50 nm) in the Raman

Final conclusion they are complementary techniques!
Interpretation of IR and Raman Spectra
General Features:
Stretching frequencies are greater (higher wavenumbers) than
corresponding bending frequencies
It is easier to bend a bond than to stretch it
Bonds to hydrogen have higher stretching frequencies than those
to heavier atoms.
Hydrogen is a much lighter element
Triple bonds have higher stretching frequencies than double
bonds, which have higher frequencies than single bonds
Strong IR bands often correspond to weak Raman bands and
vice-versa
Interpretation of IR and Raman Spectra
Characteristic Vibrational Frequencies for Common Functional Groups
Frequency (cm
-1
) Functional Group Comments
3200-3500 alcohols (O-H)
amine, amide (N-H)
alkynes (CC-H)
Broad
Variable
Sharp
3000 alkane (C-C-H)
alkene (C=C-H)
2100-2300 alkyne (CC-H)
nitrile (CN-H)
1690-1760 carbonyl (C=O) ketones, aldehydes,
acids
1660 alkene (C=C)
imine (C=N)
amide (C=O)
Conjugation lowers
amide frequency
1500-1570
1300-1370
nitro (NO
2
)
1050-1300 alcohols, ethers,
esters, acids (C-O)
IR and Raman Spectra of an Organic Compound
The IR and Raman spectra of
flufenamic acid (an analgesic/anti-
inflammatory drug):
CF
3
O OH
FT-IR Flufenamic acid Aldrich as recd
0.05
0.10
0.15
0.20
0.25
0.30
A
b
s
FT-Raman Flufenamic acid Aldrich as recd
0
10
20
30
40
50
60
I
n
t
500 1000 1500 2000 2500 3000 3500
Raman shift (cm-1)
IR and Raman Spectra of an Organic Compound
The IR and Raman spectra of
flufenamic acid (an analgesic/anti-
inflammatory drug):
CF
3
O OH
FT-IR Flufenamic acid Aldrich as recd
0.05
0.10
0.15
0.20
0.25
0.30
A
b
s
FT-Raman Flufenamic acid Aldrich as recd
0
10
20
30
40
50
60
I
n
t
200 400 600 800 1000 1200 1400 1600
Wavenumbers (cm-1)
Note materials
usually limit IR
in this region
IR and Raman Spectra of an Organic Compound
The IR and Raman spectra of tranilast:
Tranilast Form I FV101031-171A1 FTIR
0.1
0.2
0.3
0.4
0.5
0.6
A
b
s
Tranilast Form I FV101031-171A1 FT-Raman
100
200
300
400
500
I
n
t
500 1000 1500 2000 2500 3000 3500
Wavenumbers (cm-1)
O
O
N
H
O
OH O
C1
C6 C2
C3
C4
C5
C7
N1
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
H
3
C
H
3
C
O4
O5
O3
O2 O1
IR Frequencies and Hydrogen Bonding Effects
IR frequencies are sensitive to
hydrogen-bonding strength and
geometry (plots of relationships
between crystallographic distances
and vibrational frequencies):
G. A. Jeffrey, An Introduction to Hydrogen Bonding, Oxford, 1997.
Applications of Far IR Spectroscopy
Far IR is used to study low frequency vibrations, like
those between metals and ligands (for both inorganic and
organometallic chemistry).
Example: Metal halides have stretching and bending vibrations in
the 650-100 cm
-1
range.
Organic solids show lattice vibrations in this region

Can be used to study crystal lattice energies and
semiconductor properties.

The Far IR region also overlaps rotational bands, but
these are normally not detectable in condensed-phase
work
Terahertz Spectroscopy
A relatively new technique, addresses an unused portion of the
EM spectrum (the terahertz gap):
50 GHz (0.05 THz) to 3 THz (1.2 cm
-1
to 100 cm
-1
)

Made possible with recent innovations in instrument design,
accesses a region of crystalline phonon bands
Applications of Near IR Spectroscopy
Near IR heavily used in process chemistry

Amenable to quantitative analysis usually in conjunction with
chemometrics (calibration requires many standards to be run)

While not a qualitative technique, it can serve as a fast and useful
quantitative technique especially using diffuse reflectance

Accuracy and precision in the ~2% range

Examples:
On-line reaction monitoring (food, agriculture, pharmaceuticals)
Moisture and solvent measurement and monitoring
Water overtone observed at 1940 nm
Solid blending and solid-state issues
Near IR Spectroscopy
Near IR Spectrum of Acetone
NIR taken in transmission mode (via a reflective gold plate) on a
Foss NIRsystems spectrometer
Useful for quick solvent identification
Near IR Spectrum of Water (1
st
Derivative)
1
st
derivative (and 2
nd
derivative) allows for easier identification of
bands
Photoacoustic Spectroscopy
First discovered in 1880 by A. G. Bell
The IR version of photoacoustic sampling is generally
applied to two types of system (UV-Vis spectrometry
can also be performed):

- All gas (or all-liquid)
systems:





- The solid-gas system:
Solid
IR-Transparent Gas
Gas:
IR Radiation
IR Radiation
The Photoacoustic Effect for Solid-Gas Systems
The photoacoustic effect is produced when intensity-
modulated light hits a solid surface (or a confined gas
or liquid).
Gas
Solid
Modulated IR Radiation
x
PA Cell
Thermal Wave (attenuates rapidly)
Microphone
P(x)
P
0

IR is absorbed by a vibrational transition,
followed by non-radiative relaxation
P R P e
x
R
P
surface =

( )
(
1 0
0

+ )
surface reflectivity
incident IR beam power
- absorption coefficient
- thermal diffusion length
1
|
|
|

(P
surface
)
The Thermal Diffusion Length
- The thermal diffusion length is:
PET
PVF
2

0.15 cm/sec IR 1.2 cm/sec IR
- thermal diffusion length
= / 2 t
- The thermal diffusivity a is:
- The variable e, the modulation frequency of the IR
radiation, is directly proportional to interferometer mirror
velocity, and is defined as:
(cm/sec) eter interferom Michelson of ocity Mirror vel
rs) (wavenumbe Frequency IR
4

=
M
M
v
v
v v t e
a
k
C
k
C
=

thermal conductivity
density
specific heat

e
=
2a
The Thermal Diffusion Length
- The mirror velocity is therefore inversely related to the
thermal diffusion length, and therefore can be used to
control the maximum sampling depth.

- Typical thermal diffusion lengths for the carbonyl band
(~1750 cm
-1
) of poly(ethylene terephthalate):
The thermal diffusivity was taken to be 1.3 * 10
-3
cm
2
/sec, and the absorption
coefficient of the carbonyl band was assumed to be 2000 cm
-1
.

Mirror Speed (cm/sec)

Thermal Diffusion Length (microns)

0.15 8.9
0.30 6.3
0.60 4.5
0.90 3.6
1.20 3.1

A Typical Photoacoustic FTIR Spectrum
A PA-FTIR Spectrum of a silicone sealant:
- The spectrum shows peaks where the IR radiation is being
absorbed due to vibrational energy level transitions.
IR Modulation
frequency is high
IR Modulation
frequency is low
- Differences between a PA-FTIR spectrum and a regular IR
spectrum:
IR modulation frequency effects (weak CH
3
and CH
2
bands)
Saturation of strong bands in the spectrum
Photoacoustic Saturation
Strong bands in PA-FTIR spectra
often show saturation.

Saturation occurs when the
vibrational transition is being
pumped to its excited state faster
than it can release energy.

A high absorption coefficient
coincides with faster saturation.
A Saturated Band
Depth-Profiling Studies with PA-FTIR
- Thermal diffusion length
allows for IR depth
profiling with PA-FTIR

- Example: a layer of
poly(vinylidine fluoride
(PVF
2
) on poly(ethylene
terephthalate) (PET)
PET
PVF
2

PVF
2
top layer is 6 micrometers thick.
The carbonyl band, due to the PET, is marked with a red dot ().
Data acquired with a Digilab FTS-20E with a home-built PA cell.
0.15 cm/sec IR 1.2 cm/sec IR
- thermal diffusion length
= / 2 t
Applications of FT Microwave Spectroscopy
Under development for: real-time, sensitive monitoring of
gases evolved in process chemistry, plant and vehicle
emissions, etc
Current techniques have limits (GC, IR, MS, IMS)
Normally use pulsed-nozzle sources and high-precision Fabry-
Perot interferometers (PNFTMW)
Diagram from http://physics.nist.gov/Divisions/Div844/facilities/ftmw/ftmw.html
Compound Detection Limit
(nanomol/mol)
Acrolein 0.5
Carbonyl sulfide 1
Sulfur dioxide 4
Propionaldehyde 100
Methyl-t-butyl ether 65
Vinyl chloride 0.45
Ethyl chloride 2
Vinyl bromide 1
Toluene 130
Vinyl cyanide 0.28
Acetaldehyde 1
Hybrid/Hyphenated Techniques: Interfaces
Interfaces between vibrational spectrometers and other
analytical instruments

GC-FTIR: gaseous column effluent passed through light
pipes





Similar Technique: TGA-IR, for identification of evolved
gases from thermal decomposition