RESONANCE RAMAN SPECTROSCOPY

Overview
Ø Brief introduction on Resonance Raman Scattering.
Ø Advantages of RRS.
Ø Why intensity of the scattered radiation is
enhanced?
Ø Quantum Mechanical Theory of normal Resonance
Raman Scattering.
Ø Theory of Resonance Raman Scattering.
Ø A-term Resonance Raman Scattering.
Ø B- term resonance Raman Scattering.
What is Resonance Raman Scattering?

The wave number of

the exciting radiation
is close or same with
that of an electronic
transition.
Advantages of Resonance Raman Spectroscopy.
Enhancement of intensities of partticular
bands.
High sensitivity….
Analytical tool for the study of chromophores.
Detailed information about those excited states
which raman active.
 Why intensity is enhanced?
i- is the initial
state.
f – is the final Transition Polarisibillity
tensor.

Irradianc
Wave number
e. of incident
radiation.
The above expression is the intensity of scattered radiation at
90• angle.

What is transition polarizability

tensor?
What is irradiance?
What is damping factor?
Theory of normal Raman Scattering

 Adiabatic Born Oppenheimer

approximation……??

Formed by product of the pure

vibrational
and the pure electronic state.

ØElectronic state parametrically dependent on the normal co-ordinate of the

molecule.
ØElectronic transition moment also dependent on normal co-ordinate.
The electronic and vibrational part of
the integrals can be seperated.
When excitation far from any region of
electronic absorption…..normal Raman.
The denominators in the transition polarizability
are large.

With all these approximation………..

What is the significance of each term?

Rayleigh Scattering , Raman Scattering, overtone
and combination band.
 Theory of Resonance Raman Scattering
(1)Adiabatic Born Oppenheimer approximation is
assumed to valid.

H T perturbation description to vibronic coupling……..


Variation of transition
moment
Is related with the vatriation
of
Hamiltonian with normal co-
ordinate can mix the state e
Four contribution to the transition polarizability……
What is vibronic coupling ?
Is Born Oppenheimer Approx. applicable under
strong vibronic coupling?

Brief discussion on
each
term
 A-term Resonance Raman Scattering

What are the conditions for A-term contribution to

RRS?
What is Frank Condon factor?
The technique requires the excitation within the
contour of intense absorption band.
Excitation with in the contour of weak band (like
spin forbidden transition ) would not be expected
to give significant A term.
Non-zero Vibrational overlap integral
When Vibrational wave functions are non orthogonal.
This condition arises when….there is either…

4) A difference in vibrational wave number i.e. change in

shape of the potential surface.

6) A displacement of the potential energy minimum

along normal co-ordinate.

8) This occurs only in totally symmetric modes of

vibration…….why?
Orthogonality condition is not
removed

Produces non zero overlap

integral
For both totally symmetric
and not

These two only applicable to the

totally
Symmetric mode .
 B-term Resonance Raman Scattering

Conditions :
1)vibronic coupling .
2) both resonant transition and
transitions are electric dipole
allowed.
B-term is very much smaller than A –term

üwhen A term is more important than B-term?

üWhen B term is more important than A-term?
THANK YOU