1

Lecture Date: January 30

th
, 2008
Rotational and Vibrational
Spectroscopy
Vibrational and Rotational Spectroscopy
- Core techniques:
Infrared (IR) spectroscopy
Raman spectroscopy
Microwave spectroscopy
2
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.
W. Abney, E. R. Festing, Phil. Trans. Roy. Soc. London, 1882, 172, 887-918.
3
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 Table16-1 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:
Imagefromwww.asu.edu

v
10000
1
=

cm
- Converting
wavelength () to
wavenumbers:
4
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):
SeeE. B. Wilson, J r., J . C. Decius, and P. C. Cross, Molecular Vibrations, Dover, 1955.
2 1
2 1
m m
m m
+
=
Rotational Spectroscopy: Theory
- Rotational energy levels can be
described as follows:
R. Woods and G. Henderson, FTIR Rotational Spectroscopy, J . Chem. Educ., 64, 921-924 (1987)
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:
cisthespeedof light
k istheHookeslaw forceconstant
r0isthevibrationally-averaged bondlength
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
isthereducedmass
h isPlancksconstant
e
0
=2990.946 cm
-1
(fromIR)
k =5.12436 x 10
5
dyne/cm
-1
For J =0, 1, 2, 3
5
Vibrational Spectroscopy: Theory
- Harmonic oscillator based on the classical spring
( )
m
h v E v
2
1
+ =
v
m
is thenatural frequency of theoscillator (a.k.a. thefundamental vibrational wavenumber)
k is theHookes law forceconstant (now for thechemical bond)
u
k
m
t
v
2
1
=
v is thevibrational quantumnumber
h is Plancks constant
- Since v must be a whole number (see Ex. 16-1, pg. 386):
- 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
(wavenumbers)
r is thedistance(bond distance)
r
e
is theequilibriumdistance
Vibrational Spectroscopy: Theory
- Potential energy of a harmonic oscillator:
FigurefromSkooget al.
6
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 thedissociation 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)
7
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 changeindipole
IR-inactive
Asymmetric
Changeindipole
IR-active
Scissoring
Changeindipole
IR-active
- IR-active modes require dipole changes during rotations
and vibrations!
Vibrational Modes: Examples
- IR-activity requires
dipole changes
during vibrations!
- For example, this
is Problem 16-3
from Skoog:
Inactive
Active
Active
Active
Inactive
Inactive
Active
8
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:
Formaldehydespectrumfrom: http://www.cem.msu.edu/~reusch/VirtualText/Spectrpy/InfraRed/infrared.htm#ir2
Resultsgenerated usingB3LYP//6-31G(d) inGaussian03W.
- 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.
9
The Raman Effect
- Polarization changes
are necessary to form
the virtual state and
hence the Raman
effect
- This figure depicts
normal (spontaneous)
Raman effects
H. A. Strobel andW. R. Heineman, Chemical Instrumentation: A Systematic Approach, 3
rd
Ed. Wiley: 1989.
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 andR. S. Friedman, Molecular Quantum Mechanics, 3
rd
Ed. Oxford: 1997.
10
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 andR. 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
FigureisredrawnfromD. P. StrommenandK. 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)
11
Raman-Acti ve 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 Depolarizati on 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.
12
Instrumentati on 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 J acqinot (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
13
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
FiguresfromWikipedia.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 isthefrequency of theradiation
cisthespeedof light incm/s
vmisthemirror velocityincm/s
14
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:
15
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.
Figuresfromhttp://www.nuance.northwestern.edu/KeckII/ftir7.asp
ATR
DRIFTS
16
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)
17
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.
18
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.
19
Applications of Raman Spectroscopy
- Raman in catalysis research (see C&E News, Oct. 13,
2006, pg. 59):
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) See work from the Stair group at
Northwestern
For uses of SERS: Catal. Commun 3 547 (2002).
- 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!
20
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)
Seealso Table17-2 of Skoog, et al.
Moredetailedlistsarewidelyavailable. SeeR. M. SilversteinandF. X. Webster, Spectrometric Identificationof Organic Compounds, 6
th
Ed., Wiley, 1998.
21
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 acidAldrichas recd
0.05
0.10
0.15
0.20
0.25
0.30
A
b
s
FT-RamanFlufenamic acidAldrichas recd
0
10
20
30
40
50
60
I
n
t
500 1000 1500 2000 2500 3000 3500
Ramanshift(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 acidAldrichas recd
0.05
0.10
0.15
0.20
0.25
0.30
A
b
s
FT-RamanFlufenamic acidAldrichas 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
22
IR and Raman Spectra of an Organic Compound
The IR and Raman spectra of tranilast:
Tranilast FormI FV101031-171A1FTIR
0.1
0.2
0.3
0.4
0.5
0.6
A
b
s
Tranilast FormI FV101031-171A1FT-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
H3C
H3C
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.
23
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
P. F. Taday andD. A. Newnham, Spectroscopy Europe, , www.spectroscopyeurope.com
G. Winnewisser, Vibrational Spectroscopy 8 (1995) 241-253
24
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
Figurefromwww.asdi.com. Formoreinformationsee:
1. Ellis, J .W. (1928) Molecular Absorption Spectraof Liquids Below3 m, Trans. Faraday Soc. 1928, 25, pp. 888-898.
2. Goddu, R.F and Delker, D.A. (1960) Spectra-structurecorrelations for the Near-Infrared region.Anal. Chem., vol. 32no. 1, pp. 140-141.
3. Goddu, R.F. (1960) Near-Infrared Spectrophotometry,Advan. Anal. Chem. Instr. Vol. 1, pp. 347-424.
4. Kaye, W. (1954) Near-infrared Spectroscopy; I. Spectral identification andanalytical applications,Spectrochimica Acta, vol. 6, pp. 257-287.
5. Weyer, L. and Lo, S.-C. (2002) Spectra-Structure Correlations in the Near-infrared, In Handbook of Vibrational Spectroscopy, Vol. 3, Wiley, U.K., pp. 1817-1837.
6. Workman, J . (2000) Handbook of Organic Compounds: NIR, IR, Raman, and UV-Vis Spectra Featuring Polymers and Surfactants, Vol. 1, Academic Press, pp. 77-197.
25
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
26
Photoacousti c 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
A. G. Bell, Am. J. Sci. 20 (1880)305.
A. G. Bell, Philos. Mag. 11(1881), 510.
The Photoacousti c 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)
J. F. McClelland. Anal. Chem. 55(1), 89A-105A (1983)
M. W. Urban. J. Coatings Technology. 59, 29 (1987).
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
)
27
The Thermal Diffusion Length
Urban, M. W. J. Coatings Technology. 1987, 59, 29
Quintanilla, L., Rodriguez-Cabello, J. C., Jawhari, T. andPastor, J. M.. Polymer. 1993, 34, 3787.
- The thermal diffusion length is:
PET
PVF
2
0.15 cm/sec IR 1.2 cm/sec IR
- thermal diffusion length
= / 2
- 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
Urban, M. W. andKoenig, J. L. Appl. Spec. 1986, 40, 994.
Quintanilla, L., Rodriguez-Cabello, J. C., Jawhari, T. andPastor, J. M.. Polymer. 1993, 34, 3787.
- 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):
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
Thethermal diffusivity was taken to be1.3* 10
-3
cm
2
/sec, and theabsorption coefficient of thecarbonyl band was
assumed to be2000cm
-1
.
28
A Typi cal 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.
Paroli, R. M., Delgado, A. H., andCole, K. C. Canadian J. Appl. Spectr. 1994, 39, 7.
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
Photoacousti c 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
Rosencwaig, A. Photoacoustics and Photoacoustic Spectroscopy. Wiley: New York, 1980.
Paroli, R. M., Delgado, A. H., andCole, K. C. Canadian J. Appl. Spectr. 1994, 39, 7.
29
Depth-Profiling Studies with PA-FTIR
Urban, M. W. andKoenig, J. L. Appl. Spec. 1986, 40, 994.
Crocombe, R. A. andCompton, S. V. Bio-RadFTS/IR ApplicationNote82. Bio-RadDigilabDivision, Cambridge, MA, 1991.
- 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 6micrometers thick.
Thecarbonyl band, dueto thePET, is marked with ared dot ().
Dataacquired with aDigilab FTS-20E with ahome-built PA cell.
0.15 cm/sec IR 1.2 cm/sec IR
- thermal diffusion length
= / 2
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)
Diagramfromhttp://physics.nist.gov/Divisions/Div844/facilities/ftmw/ftmw.html
For moreinformation, seeE. Arunan, S. Dev. AndP. K. Mandal, Applied Spectroscopy Reviews, 39, 131-181 (2004).
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
30
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
FigurefromSkooget al.
Homework Problems
Chapter 16:
16-7
Chapter 18:
18-2
31
Further Reading
L. J . Bellamy, Advances in Infrared Group Frequencies, Methuen and Co.,
1968.
R. M. Silverstein and F. X. Webster, Spectrometric Identification of Organic
Compounds, 6
th
Ed., Wiley, 1998.
P. W. Atkins and R. S. Friedman, Molecular Quantum Mechanics, 3
rd
. Ed.,
Oxford, 1997.