Raman Spectroscopy

This is another photon in photon out spectroscopy, which detects vibrational

motion of the atoms/ groups of atoms in a molecule.
The photon in possesses energy in the visible wavelength window.
This photon is scattered by the sample either elastically (Rayleigh) or
inelastically (Raman).
The inelastic part of the scattering is ~10-6 of the elastic component.
This poses a tough problem and, hence, Raman spectra are difficult to detect.
It is only with the use of present day monochromatic laser sources and sensitive
detectors that it is possible to use Raman spectroscopy as a routine analytical tool.

A typical Raman apparatus looks as follows:

Sample
Laser
Spectrometer
Scattered light

' 0

' 0

' 0

Scattering arises when electrons in a molecule oscillate in sympathy with an applied

electromagnetic wave.
The extent of scattering depends on the polarizability of the electron in the molecule.
Most of the oscillating electrons scatter at the same frequency as the incident beam
(Rayleigh). However , during the time that the electrons oscillate, a vibration may
occur that causes some of the energy of the incident light to be transferred to the
molecule (or vice versa ).

Since the energy is quantized, the transfer or acceptance of energy by the

molecule must correspond to a difference (E) between the energy levels of the
molecule.
- Thus, the value of E is independent of the frequency of the exciting light.
The Raman scattering (inelastic component) is of two parts:
Stokes and Anti-Stokes -depending on the starting energy of the molecule
(group of atoms ).
Stokes lines are usually measured since they are of higher intensity.

The representation of the processes that are involved in Raman scattering are
shown below.
Excited
electronic state

Virtual energy levels

Anti-Stokes
Ground electronic
state

Stokes

IR Raman Rayleigh Raman

Preresonance
Raman

Resonance
Raman

Fluorescence

Figure: Processes leading to normal, preresonance, and resonance Raman scattering. (For comparison,
the processes involved in IR and fluorescence are shown.) .The horizontal lines represent different
vibrational energy levels in the two electronic states. The Raman scattering spectrum is also indicated.
Note that the intensity of the Stokes lines are greater than that of the anti-Stokes.

The selection rule for Raman scattering is that the vibrational motion produces a
change in the polarizability of the molecule.
(The intensity of the Raman band is proportional to the square of the
derivative of the polarizability).
This is in contrast to IR spectroscopy where a change in dipole moment has to
occur.
(The intensity of the IR band is proportional to the square of the derivative
of the dipole moment.)
The no. of vibrations that are active in the Raman and IR can be determined by
group theory- symmetry analysis of the molecule.
e.g., for a centero-symmetric molecule there are no vibrations that are active both
in the Raman and IR spectra - Principle of mutual exclusion.
(A centero-symmetric molecule is one which possesses a center of symmetry, i.e.,
at the center of symmetry (0,0,0), for every atom at (x,y,z) there is an identical
atom at (-x,-y,-z).

LASER RAMAN SPECTROSCOPY

High symmetry

IR

Low symmetry

IR

Point group C2h ,D8h

e.g., CO2,transCHCl=CHCl
Point group C2v, C3v
e.g., pyridine, CH3Cl
Point group C1, C2
e.g., CHFClBr, H2O2

To determine the complete vibrations of a centero-symmetric molecule the Raman

and IR spectra are both required.
In molecules in general, the IR and Raman spectra combined give a better picture of
the structure of the molecule and the two are considered to be complementary.
-Usually the stretching vibrations are more intense in the Raman
compared to the IR and in the IR asymmetric stretch is more intense.

APPLICATIONS:
(A) Bulk Structure:
Zeolites have been successfully investigated and wavenumbers down to 100 cm -1
have been observed. The most intense bands of zeolites appear to the Si-O-Si
bending mode. The asymmetric stretching mode of the Si-O-Si which is intense in
the IR is absent in the Raman spectrum.
Transition metal oxides as catalysts are the most successfully studied Raman
spectroscopy, e.g., CoO3-MoO3 supported on Al2O3is an important catalyst for the
HDS of crude oil.
Raman bands associated with Mo-O-Mo at 877 cm-1 & Mo-O terminal bands at
948 cm-1 were observed, which are similar to the Raman bands associated with
MoO3/Al2O3. These results suggest that Mo-oxide phase is independent of the Cooxide phase.

(B) Adsorption of C6H6 on SiO2 has been studied by Raman spectroscopy.

The ring breathing mode at 994 cm-1 is reduced substantially upon adsorption.
From IR spectroscopy it is observed that the Si-OH band also decreasing
suggesting that the ring electrons interact with the Si-OH group.

( C ) Adsorption Sites and structure of adsorbed species:

Pyridine is widely used for Raman and IR studies in examining the properties of
adsorbate- adsorbent interaction. Pyridine is a base and is used for studying the
acidity (Lewis, electron accepting, and Bronsted, proton donating, properties) of
surfaces. It is a heterocyclic amine with a pair of unshared electrons on the nitrogen
atom.
14

Figure: Adsorbable surface coverage for pyridine adsorbed silica gel: pressures are indicated in torr. From Schrader
and Hill[31].