Raman Spectroscopy

Light Scattering
1. Raleigh molecule
2. Tyndall particle with size 1 1,5 x
"for his work on the scattering of light and for the discovery
of the effect named after him"
The Nobel Prize in Physics 1930
Sir Chandrasekhara Venkata Raman
Sir C.V. Raman during a lecture at the Raman
Research Institute in Bangalore, circa 1959.
Scattering of Radiation:

C. V. Raman discovered that the
wavelength of a small fraction of radiation
scattered by certain molecules differs from
that of the incident beam. The shifts in
wavelength depend on the chemical
structure of the molecules responsible for
the scattering.
Raman Scattering

Raman Scattering:

Results from the same type of quantized vibrational changes
that are associated with IR absorption.

The difference in wavelength between the incident and
scatteredradiation corresponds to the mid-IR region.

The Raman scattering spectrum and IR absorption spectrum
of a compound often closely resemble each other. But there
are enough differences in the kinds of groups that are IR and
Raman active that the techniques are complementary.
Energy level diagram

Raman Spectrum

Raman Spectroscopy
Number of peaks related to degrees of freedom
DoF = 3N - 6 (bent) or 3N - 5 (linear) for N atoms
Energy related to harmonic oscillator

Selection rules related to symmetry
Rule of thumb: symmetric=Raman active, asymmetric=IR
active
Raman: 1335 cm
1

IR: 2349 cm
1

IR: 667 cm
1

CO
2


o or Ao =
c
2t
k(m
1
+m
2
)
m
1
m
2
Raman + IR: 3657 cm
1

Raman + IR: 3756 cm
1

Raman + IR: 1594 cm
1

H
2
O
CO
2
Vibration

Raman active and inactive

Types of Scattered Radiation:

Rayleigh wavelength is exactly same as excitation source
and is significantly more intense than other two types.

Stokes Raman scattering at longer wavelengths (lower
energy) than excitation wavelength. (Same as in
fluorescence.)

Anti-Stokes Wavelengths shifted to higher energies
(shorter wavelengths). Generally much less intense than
Stokes lines, so Stokes part of the Raman spectrum is
usually used.

The magnitude of Raman shifts are independent of the
wavelength of excitation.
Example of Raman Spectrum of CCl
4

Source: Skoog, Holler, and Nieman, Principles of Instrumental Analysis, 5
th
edition, Saunders College Publishing.
Raman scattering differs
from Rayleigh by AE, the
energy of the first
vibrational level of the
ground state.
Thus the Raman frequency
shift and the IR absorption
peak frequency are
identical.
Source: Skoog, Holler, and Nieman, Principles of Instrumental Analysis, 5
th
edition, Saunders College Publishing.
Raman Shift
Ao = o
incoming
- o
scattering
(cm
-1
)


= 1/
incoming
(cm) 1/
scattering
(cm)

Raman is caused by polarizability
Polarizability value decrease by
- increase in electron density
- increase in bond strength
- decrease in bond length
1
Instrumentation

Raman Instrumentation:

Source general laser. Chose wavelength to
avoid absorption (except Resonance
Raman), fluorescence, or
photodecomposition.

Sample-Illumination Systems since visible
frequencies, can use glass optical
components.
Raman Scattering Condition
1. Raman Intensity usually 10
-5
10
-7
times lower
than incoming light intensity, so that high
intensity light source in needed
2. Raman lines should separate from
fluorescence light, so light source in UV
wavelength is needed
3. Raman lines close to excitation and also close
together, therefore high resolution
monochromator is needed

a suitable light source is laser
Outer cavity System
Inner cavity laser
Inner Cavity
Micro cell
Micro cell

Differences between Raman and IR
Spectra

Both depend on same vibrational modes. IR
requires change in dipole or charge distribution
associated with it. Scattering is momentary
distortion of electrons followed by reemission of
radiation. The effectiveness of a bond toward
scattering depends on its polarizability (ease at
which electrons can be distorted from normal
position). Therefore Raman requires a change in
polarizability.

Advantage of Raman over IR:

Water does not cause interference in
Raman, so Raman spectra can be
obtained from aqueous solution.

Also, glass or quartz cells (rather than
NaCl or KBr disks) can be used.
Raman versus IR spectra
Depolarization Ratio
p ~ 0.75 asymmetric vibration

5. The following Raman data were obtained for CHCl
3
with the
polarizer of the spectrophotometer set
(1) parallel to the plane of polarization of the laser and
(2) at 90 deg to the plane of the source.
Calculate the depolarization ratio and indicate which Raman peak
asymmetrical stretching


No.

Ao, cm
-1

Relative Intensities
(1) I
//
(2) I

(a)
(b)
( c )
(d)
760
660
357
258
0.60
8.4
7.9
4.2
0.46
0.1
0.6
3.2
Applications of Raman Spectroscopy:

Not as wide-spread as IR.

Inorganics and Biologicals since can use aqueous solutions.

Organics advantage for double-bond stretching vibrations
that are weak IR absorption bands. Therefore more information
about olefins than IR.
Application
1. Inorganic compound, better than IR since
water is used as solvent and vibration of
metal-ligand exist between 100 700 cm
-1
, the
vibrations are commonly IR inactive

2. Organic compound, complement of IR

3. Biology, small sample, water does not affect


What are the Applications of Raman
Spectroscopy?
1. Chemical Systems e.g.,
identification, analysis, and
characterization of organics,
inorganics, including solvents,
petrochemicals, carbon
materials and films.

3. Pharmaceuticals
e.g., identification and analysis
of drug constituents, critical
additives, excipients, drugs of
abuse, quality control of the
purity and quality of
pharmaceuticals.
2. Chemical Processes e.g.,
following polymer formulations
and polymerization processes,
measuring/quantification of
multiple components in a
mixture (including solvent
mixture and aqueous solutions)
in real time, identification of
organic contaminants,
following immediate and final
product of a hydrogenation
reaction, predicting the
morphological properties of
polymers.
What are the Applications of Raman
Spectroscopy?
4. Polymers and Plastics
e.g., quality control of
incoming/outgoing products,
identification of contaminants
during manufacturing, real
time monitoring of
polymerization reactions,
multivariate
analysis/Chemometrics to
predict physical properties
such as birefringence,
crystallinity, glass transition
temperature, crystallization
temperature etc.
5. Biological and Medical
Systems
e.g., measuring the
concentrations of total protein
and biological analytes in
blood and serum, determining
metabolic concentrations,
measuring blood and tissue
oxygenation, molecular-level
cancer (cervical, lung, etc.)
and cardiovascular disease
(such as atherosclerosis)
diagnosis.

What are the Applications of Raman
Spectroscopy?
6. Food Products

e.g.,measuring the fatty acid
unsaturation in food oils,
detecting
bacteria/contaminants in
food products, identification
of additive drugs in
nutraceuticals and fruit
drinks.

7. Forensic applications e.g.,
identification and analysis of
explosives, inflammables,
toxic solvents, additive
drugs, drugs of abuse, bio-
warfare agents, and inks
from documents.
8. Materials,
Semiconductors,
Gemological, Geological,
Archaeological, and
Environmental Sciences,
etc.

Problems
1. At what wavelengths in nm would the Stokes and anti-Stokes Raman lines
for carbon tetrachloride (Ao = 218, 314, 459, 762, and 790 cm
-1
) appear if
the source was
(a) a helium/neon laser (632.8 nm)? (b) an argon ion laser (488.0 nm)?
2, Compare the relative intensities of one of the CCl
4
Raman lines when each
of the two excitation sources described in Problem 1 is used.
3. Under what circumstances would a helium/neon laser be preferable to an
argon ion laser as a Raman source?
4. For viibrational states, the Boltzmann equation can be written as

N
1
/N
0
= e
-AE/kT


where No and N1 are the populations of the lower and higher energy states
respectively, AE is"the energy difference between the states, k is
Boltzmann's constant, and T is the temperature in K.
For temperatures of 20 and 40C, calculate the ratios of the intensities of
the anti-Stokes and Stokes lines for CCl
4
at
(a) 218 cm
-1
. (b) 459 cm
-1
. (c) 790 cm
-1
.
Problem
1 Should the nitrogen molecule absorb in the IR? Should it be
Raman-active? Why?
2 Which of the following vibrational modes in the molecules given
will be IR-active, Raman-active, or both: (a) symmetric stretch of
O
2
, (b) asymmetric stretch of CO
2
, (c) bending mode in H
2
0, (d)
twisting mode in C
2
H
4
?
3 The IR spectrum of carbon tetrachloride contains one
fundamental absorption peak at 790 cm
-1
. The Raman spectrum
of CCl
4
shows fundamental vibration peaks at wave number shifts
of 218, 314, 459, and 790 cm-1. Explain the absence of the first
three peaks in the IR spectrum.
4 In the Raman spectrum of a compound obtained with He-Ne laser
excitation lines are observed at 650.0 661.5, and 670.3 nm.
Calculate the wavenumber shift (Ao) of each line.
5 Why is Raman spectroscopy considered to be superior to IR
spectroscopy for the analysis of many organosulfur compounds
such as sulfides, disulfides, and thiophenes?
Answer
1. No; yes.
2. (a) Raman-active, (b) IR-active, (c) both,
(d) neither.
5.Sulfur is a highly polarizable substituent
atom, so it produces a highintensity
Raman signal. Sulfur-carbon bonds do not
produce an especially strong dipole,
however, so the corresponding IR bands
are weak.