Raman Spectra

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Theory of
Raman Spectroscopy
V.Santhanam
Department of Chemistry
SCSVMV
Fate of the Radiation Falling on a Sample
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Light and Spectroscopy

• Light interacts with matter in different ways,
transmitting through some materials, while
reflecting or scattering off others.
• Both the material and the colour
(wavelength) of the light affect this
interaction.
• We call the study of this light ‘spectroscopy'.
Which parts of the visible spectrum enter our
eyes determines which colours we perceive.
What is Raman Spectroscopy?
• Raman spectroscopy is an analytical

technique where scattered light is used to
measure the vibrational energy modes of a
sample.
• It is named after the Indian physicist C. V.
Raman who, together with his research
partner K. S. Krishnan, was the first to
observe Raman scattering in 1928.
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• Raman spectroscopy can provide both

chemical and structural information, as well
as the identification of substances through
their characteristic Raman ‘fingerprint’.
• Raman spectroscopy extracts this
information through the detection of Raman
scattering from the sample.
What is Raman Scattering?
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Raman Scattering
• When light is scattered by molecule, the
oscillating electromagnetic field of a photon
induces a polarization of the molecular
electron cloud.
• This leaves the molecule in a higher energy
state with the energy of the photon
transferred to the molecule.
• This can be considered as the formation of a

very short-lived complex between the
photon and molecule which is commonly
called the virtual state of the molecule.
• The virtual state is not stable and the photon
is re-emitted almost immediately, as
scattered light.
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Rayleigh Scattering
• In the vast majority of scattering events, the
energy of the molecule is unchanged after its
interaction with the photon.
• The energy, and therefore the wavelength, of
the scattered photon is equal to that of the
incident photon.
• This is called elastic (energy of scattering
particle is conserved) or Rayleigh scattering
and is the dominant process.
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Raman Scattering
• In a much rarer event (approximately 1 in 10
million photons)Raman scattering occurs, which
is an inelastic scattering process with a transfer
of energy between the molecule and scattered
photon.
• If the molecule gains energy from the photon
during the scattering (excited to a higher
vibrational level) then the scattered photon
loses energy and its wavelength increases which
is called Stokes Raman scattering (after G. G.
Stokes).
• Inversely, if the molecule loses energy by relaxing to a

lower vibrational level the scattered photon gains the
corresponding energy and its wavelength decreases;
which is called Anti-Stokes Raman scattering.
• Quantum mechanically Stokes and Anti-Stokes are
equally likely processes.
• However, with an ensemble of molecules, the
majority of molecules will be in the ground
vibrational level (Boltzmann distribution) and Stokes
scatter is the statistically more probable process.
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• As a result, the Stokes Raman scatter is always

more intense than the anti-Stokes and for this
reason, it is nearly always the Stokes Raman
scatter that is measured in Raman spectroscopy.
• The wavelength of the Raman scattered light will
depend on the wavelength of the excitation light.
• This makes the Raman scatter wavelength an
impractical number for comparison between
spectra measured using different lasers.
Raman Shift
• The Raman scatter position is therefore
converted to a Raman shift away from
excitation wavelength
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Raman Spectrum of CCl4
Classical Theory of Raman Effect

• When an electrically neutral molecule is kept
in an uniform electrical field, it is polarized.
• The extent of polarization is given by the
induced dipolemoment
μ= α . E
α – Polarizability of the molecule
A second degree tensor
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Classical Theory of R.E

• When a radiation of frequency ν is falling on
a molecule, the electrical field felt by the
molecule is
E  E 0 sin 2  t
• This electrical field polarizes the molecule
and makes it to oscillate with the same
frequency.
• The associated induced dipole moment is
   .E  E0 sin 2t
• Such an oscillating dipole emits radiation of

its own oscillation frequency, which is called
Rayleigh Scattering
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Classical Theory of Raman Effect
Raman Scattering
• If the molecule undergoes rotation or
vibration also, then the polarizability of it
changes, hence the emitted frequencies also -
Raman Scattering.
• Lets assume that the polarizability of the
molecule α is changed by the vibartional
frequency of the molecule νvib
   0   sin 2 vibt
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   0   sin 2 vibt

Where,
- α0 is the equilibrium polarizability
- β is the rate of change of polarizability with vibration
- νvib is the vibrational frequency
  E  ( 0  sin 2 vib t ) E0 sin 2t

- By expansion and using the relation,
1
SinA.SinB  [cos( A  B )  cos( A  B )]
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1
   0 E0 sin 2t  E0 [cos 2 (  vib )t  cos 2 (  vib )t ]
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Above equation shows that the oscillating dipole has

three frequency components namely,
-ν Rayleigh Line
- (ν+ νvib) Raman Line ( Anti-Stokes)
- (ν- νvib) Raman Line (Stokes)
• The Raman shift is depending on the β value.
• If the polarizability change with vibration is zero
then the Raman shift is also zero, i.e. the vibration is
not Raman active.
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Quantum Theory of Raman Effect
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Raman Activity
• When a vibration is Raman active?
The polarizability ellipsoid should change in
– Shape
– Size
– Orientation
Polarizability Ellipsoid
• 3D figure created by tracing the values of
(1/√α)
• For many molecules α is different in different
directions – anisotropic.
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Rotational Raman
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Mutual Exclusion Rule

• It states that no normal modes can be
both Infrared and Raman active in a molecule
that possesses a centre of symmetry
• This is a powerful application of group
theory to vibrational spectroscopy, and
allows one to easily detect the presence of
this symmetry element by comparison of the
IR and Raman spectra generated by the same
molecule.
Group Theoretical Explanation

• The rule arises because in a centrosymmetric point
group, IR active modes, which must transform
according to the same irreducible
representation generated by one of the components
of the dipole moment vector (x, y or z), must be
of ungerade (u) symmetry, i.e. their character under
inversion is -1,
• while Raman active modes, which transform
according to the symmetry of the polarizability tensor
(product of two coordinates), must be of gerade (g)
symmetry since their character under inversion is +1.
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• In the character table there is no irreducible

representation that spans both IR and
Raman active modes, and so there is no
overlap between the two spectra.
Mutual Exclusion Principle - violations

• This does not mean that a vibrational mode
which is not Raman active must be IR active.
• In fact, it is still possible that a mode of a
particular symmetry is neither Raman nor IR
active.
• Such spectroscopically "silent" or "inactive"
modes exist in molecules such
as ethylene (C2H4), benzene (C6H6) and
the tetrachloroplatinate ion (PtCl42−).
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Raman Spectra

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28-02-2021

Fate of the Radiation Falling on a Sample

Light and Spectroscopy

What is Raman Spectroscopy?

• Raman spectroscopy is an analytical

• Raman spectroscopy can provide both

What is Raman Scattering?

• This can be considered as the formation of a

• Inversely, if the molecule loses energy by relaxing to a

• As a result, the Stokes Raman scatter is always

Raman Spectrum of CCl4

Classical Theory of Raman Effect

Classical Theory of R.E

• The associated induced dipole moment is

   .E  E0 sin 2t

• Such an oscillating dipole emits radiation of

Classical Theory of Raman Effect

   0   sin 2 vibt

   0   sin 2 vibt

  E  ( 0  sin 2 vib t ) E0 sin 2t

Above equation shows that the oscillating dipole has

Quantum Theory of Raman Effect

Mutual Exclusion Rule

Group Theoretical Explanation

• In the character table there is no irreducible

Mutual Exclusion Principle - violations

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