Analytical Instrumentation:

Raman Spectroscopy

Introduction
Sometimes called as Raman effect.
Discovered in 1928 by Sir. C.V.
Raman.
Was awarded the Nobel prize in physics
in 1930.
Was and remains the shortest time from
discovery to awarding of the prize.

Features
Powerful analytical tool for the
quantitative analysis of complex
mixtures,
for
locating
various
functional groups or chemical bonds
in molecular structure.
The fields of application are quite
diverse and include polymers, paints,
semiconductors, corrosion, medicine,
biology, ceramics, catalysis, and
photochemistry, etc..

Rayleigh Scattering
When a sample is irradiated with
monochromatic light in the visible
region, majority of the light simply
passes through the sample in the
direction of incident beam.
Small portion is scattered by the
sample in all direction, which can be
observed by viewing the sample at
right angles to the incident beam.
Shown by Lord Rayleigh in 1871.

Rayleigh Scattering

Raman Effect
About 1% of the total scattered
intensity occurs at frequencies that
are different from the incident
frequency.
Called Raman Scattering.
Is inelastic.
Light photon lose or gain energy during
the scattering processes, and therefore
increase or decrease in wavelength
respectively.

Energy

Rayleigh
Scattering
(elastic)
Virtual State

IR
Absorption

Anti-Stokes
Scattering

Stokes
Scattering

h0
h0

h0

h0

h0+hm

h0hm
E0+hm
E0

Raman Scattering

Raman
(inelastic)

E-hvm

IfIf the
from a
the molecule
moleculeisispromoted
in a vibrational

ground
to begin
virtual with,
state, and
and after
then
state to
drops
backis down
to a (higher
scattering
in its ground
state,
energy)
vibrational
state
than has
the
then the
scattered
photon
scattered photon has less energy
more energy.
than the incident photon.
Shorter wavelength.
Longer
wavelength.

Antistokes
scattering.
Stokes
scattering.

fre
q

Theory of Raman
Spectroscopy

Theory of Raman
Spectroscopy

Theory of Raman
Spectroscopy

Antistock
Rayleigh
Stock Scattering
Scattering
Frequency is
No
Frequency
frequency
is
decreased
increased
change

Raman Spectrometer
Raman intensities
incident radiation.

are

approximately

0.01%

of

the

Intensity of Raman lines is much weaker than the exciting lines.

Spectrometer must employ intense source of radiation, sensitive
detector, high light gathering capability.
Excellent optical system would be needed to ensure stray light
rejection.
o Important if it is required to measure close to the Rayleigh line.
o Achieved by using two or monochromators.

Raman spectrum can be recorded by using two methods:

1) Focus the spectrum from monochromator onto a photographic
plate. Measure the light frequency and intensity using external
equipment after the plate is developed.
2) Focus the spectrum from the monochromator onto a
photomultiplier tube, and the detected signal is amplified.
Advantage is that the response to Raman line is linear.

The major components

in a Raman system
are:

Raman Spectrometer

Laser as an excitation
source.
Sample
compartment
and associated optics.
Spectrometer/
monochromator.
Detector system.

Raman Spectrometer:
Source
Is laser, due to their highly monochromatic nature, and high
beam fluxes.
Helium-Neon laser, which emits 632.8nm, is a commonly
used excitation in the modern Raman spectrometer.
In red region of the spectrum, there is a loss of intensity.
Can be overcome by using laser with power output in the range of 5-30mW.

Usually the Raman spectrum cannot be obtained if the

sample absorbs the wavelength.
At 632.8nm, fewer samples have absorbance.

Another difficult in Raman spectroscopy is that of the

sample fluorescence when irradiated.
The spectrum observed would be the fluorescence spectrum.
Red wavelength is frequently less effective in generating
fluorescence.

Raman Spectrometer:
Source
Argon-ion (visible) laser is the most
commonly used source in Raman
spectroscopy.
Tunable dye laser is increasingly
used in visible and UV laser.
The type of laser required depends
upon the sample, and the Raman
technique to be used.
Specified Raman methods may
sometimes involves the simultaneous

Raman Spectrometer:
The Detector

BAND INTENSITIES

METHANE
Raman intensities may be
quite different than those
of the IR spectrum, often
the opposite to those of IR.
Some IR bands may be
missing from the Raman,
and vice versa.

For a vibrational mode to

be IR active, the vibration
must cause a change in
the dipole moment of the
molecule.
For a vibrational mode to
be Raman active, the
vibration must cause a
change in the polarizability
of the molecule.

Rule of Mutual Exclusions

If a material has a center of
symmetry, then Raman
active vibrations are IR
inactive, and vice-versa.
560cm-1

1480cm-1

2565cm-1

Rule of Mutual Exclusions

If a material has a center of
symmetry, then Raman
active vibrations are IR
inactive, and vice-versa.
1594cm-1

3656cm-1

3755cm-1

With IR spectroscopy

COMPARISON

Differences and Complementary Power

of Infrared and Raman Spectroscopy
Infrared

Raman

Physical effect

Absorption
Scattering
Changing
of
the Changing
of
the
dipole (strong ionic
polarizability (strong
bond like O-H, N-H).
covalent bondings like
C=C, C-S, S-S)

Sample preperation

Optimal
thickness No
contact,
no
(transition mode) or
destruction,
simple
sample contact mode
preperation (if only)
Water as solvent or
(ATR) necessary
glass as container do
not
disturb
the
measurement

Problem

fluorescence

Materials

Mainly
compound

Chemical imaging

Mapping

organic Nearly unlimited

Mapping
imaging

and

global

Thank You!