Raman Spectroscopy

Chapter 18, pp 481

Introduction
C.V.Raman, Indian Physicist, 1928
visible l of a small fraction of radiation
scattered by certain molecules
differ from the incident beam

shifts in l depend on chemical structure of

the molecules responsible for the scattering

Introduction
Raman spectroscopy
measurement of the wavelength and intensity of
inelastically scattered light from molecules.
Raman scattered light occurs
at wavelengths that are shifted from the incident
light by the energies of molecular vibrations.

Introduction
the mechanism of Raman scattering is different from
that of infrared absorption.
Raman and IR spectra provide complementary
information.
Typical applications are in structure determination,
multicomponent qualitative analysis, and quantitative
analysis.

Introduction
compliments IR techniques
Advantages
water is a useful solvent
signals usually in the visible or near IR region, can
use glass or quartz cells
avoid working with NaCl or other atmospherically
unstable window materials

Theory
Raman spectra
irradiating a sample with a powerful laser source of visible or
near IR monochromatic radiation

Irradiation (process)
the spectrum of the scattered radiation is measured at some
angle (often 90o) with a suitable spectrometer (figure 18-6,
pp487)

To avoid fluorescence

the excitation ls are usually well removed from an absorption

band of the analyte

Inelastic Scattering
Figure 6-18, pp 149

scattered radiation
Ps

sample
Incident radiation
Po

 Incident radiation of frequency, ex , impinges on the

sample
sample molecules are excited from one of their ground
vibrational states to a higher so-called virtual state (dashed
line)

When the molecule relaxes, it may return to the 1st

vibrational state & emit a photon of energy
E = h (ex - v)

where v is the frequency of the vibrational transition

 Alternatively, if the molecule is in the 1st excited

vibrational state, it may absorb a quantum of the
incident radiation, be excited to the virtual state, relax
back to the ground vibrational state.

E = h (ex + v)
In both cases emitted radiation differs in frequency from the
incident radiation by the vibrational frequency of the
molecule v.

 the intensities of the stokes and anti stokes peak give

quantitative information.
the positions of the peaks give qualitative information
about the sample molecule.

 When scattered radiation is of lower frequency than the

excitation radiation Stokes scattering
Scattered radiation of a higher frequency than the source
radiation anti-Stokes scattering

Raman spectrum
of CCl4 excited by
laser radiation of
lex = 488 nm

Elastic scattering can also occur with emission of a photon

of the same energy as the excitation photon, hex
Scattering radiation of the same frequency as the source
Rayleigh scattering

 Raman spectra, abscissa, wavenumber shift,

definition

difference in wavenumbers (cm-1) between the

observed radiation & that of the source
Raman scattering require there be a change in
polarizability during vibration
polarizability is a measure of deformability of the
bond in an electric filed

Raman spectrum of CCl4

excited by laser radiation of
lex = 488 nm

Magnitude of Raman shifts is independent of the l of the

excitation
Raman shifts for CCl4 is identical regardless excitation with
argon-ion laser (488.0 nm) or helium-neon laser (632 nm)
Note: ratio of anti-stokes to stokes intensities increases
with temperature bcoz larger fraction of the molecules is in
the 1st vibrational excited state under these circumstances

Instrumentation

Instrumentation

Modern Raman spectroscopy

laser source
sample illumination system
suitable spectrometer

Source: http://research.pbsci.ucsc.edu/chemistry/li/teaching/chem268/Spectroscopic%20techniques.pdf

Instrumentation: Sources

Sources nearly always lasers

High intensity necessary to produce Raman

scattering of sufficient intensity to be measured with
a reasonable signal S/N ratio

Instrumentation: Sample-illumination System

Sample handling for Raman Spectroscopy
measurement is simpler than IR
Can use glass for windows, lenses and other optical
components
Common sample holder for non-absorbing liquid
samples ordinary glass-melting-point capillary

Optical diagram of an FT-Raman instrument