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3. Raman Spectra
3.1 Introduction: When a strong beam of visible or ultra violet light illuminates a gas, a
liquid or a transparent solid, a small fraction of light is scattered in all directions. The
scattered light is composed of photons having higher, lower or of same frequency as the
frequency of incident photons.
If the frequency of scattered light is same as of incident line than such lines are called as
Rayleigh Lines.
If the frequency of scattered light is less than as of incident line than such lines are called
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as Stokes Lines.
If the frequency of scattered light is less than as of incident line than such lines are called
as Anti-Stokes Lines
The Stokes and anti- stoke lines in combination are called as Raman lines. The stoke and
anti-stoke are equally displaced from the Rayleigh line.
Rayleigh line
zi
Stoke line
Anti-Stoke line
S 0 A cm-1
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Important properties
(i) The displacement (cm-1) of the Raman lines from the Rayleigh line (exciting lines) are
called Raman shift and it is Independent of the frequency of incident Lines.
(ii) The Raman shift only depends on the type of substance. For different scattering
substances, the Displacement has different magnitudes.
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3.2 Classical theory of Raman Effect
When a beam of visible or ultra violet light falls on a molecule the rapidly oscillating E-
field of incident radiation induces an oscillating electric dipole moment in the molecule
irrespective of whether the molecule has a permanent dipole moment or not. According to
the classical electrodynamics the oscillating dipole moment produced electromagnetic
wave.
Let E-field of light is E = Eosin2πυt and induce dipole moment is P = αE = α Eosin2πυt,
where α is Polarizability of the molecule. The molecule radiate electromagnetic waves of
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frequency υ same as of incident frequency. This phenomenon is called Rayleigh
scattering.
Polarizability depends on vibrational and rotational motion of nuclei
(a) The vibrational variation in polarizability is
α = αov + αivsin2πυosct
where αov is value of α in equllibrium. And αiv is maximum change in α
(b) The rotational variation induces
zi
α = αor + αirsin2π(2υros)t
Induce dipole moment in both case
1
Pv = αE = αovEosin2πυt + 2 αivEo[cos2π(υ – υosc)t – cos2π(υ + υosc)t]
1
and Pr = αorEosin2πυt + 2 αirEo[cos2π(υ – υrot)t – cos2π(υ + υrot)t]
Thus induce moment changes not only with the υ of incident light, but also with the
(υ – υosc), (υ + υosc), (υ – 2υrot) and (υ + 2 υrot)
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Failure of the classical theory
(i) According to classical theory, the Raman lines on the two sides must be of same
intensity. Actually, anti-stoke are weak.
(ii) While υosc has a fixed value, υrot can classically take any value. therefore the rotational
Raman spectrum must be continuous.
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3.3 Quantum Theory
Let the Energy of the incident photon, E =hυ
and Energy of the molecules (stationary), E’’.
If the collision is elastic, the molecule remains
in its initial energy state and photon scattered
with same frequency (υ). This process is called
Raleigh Scattering
If the collision is inelastic E
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(a) The molecule in the initial state E’’ take
Stokes Anti-stokes
energy and excite to E’. Lines
Photon scattered by hυ – ΔE energy
where ΔE = E’ – E’’
h E
This gives “Stoke Line” with wave Number
hc
(b) In the other case, if the molecule was initially in a higher state E’ and is transferred to
E’’ by the collision, the scattered photon emerges with increased energy hυ + ΔE.
zi
h E
This gives “Anti-Stoke lines” with wave number
hc
E
Thus the wave number shifts for stoke line is and the wave number for
hc
E
Anti-Stoke line is= . This shift is called “Raman Shift”
hc
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The number of molecules in E’ (excited state) is always less than E’’. Therefore Intensity
of Anti-Stoke is less than the Stoke lines.
In the case of free molecules ΔE which is added or given up by the molecule may be the
vibrational or rotational energy. This gives either a vibrational or rotational Raman
Spectrum.
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3.3.1 Vibrational Raman Spectrum
Selection Rule: - v 1
(The vibrational Raman spectrum thus consist of two lines at wave number given by
Raman 0 v 3 / 2 v 1/ 2 0
where 0 is wave number correspond to Raleigh line ω is vibrational constant.
hc
Anti stokes Intensity
ks
e KT
stokes Intensity
The vibrational Raman shift is Raman
3.3.2 Pure Rotational Raman Spectrum:
Selection rule: - ΔJ = 0, ±2
ΔJ = 0 gives Raleigh lines
ΔJ = +2 gives Stokes lines
zi
ΔJ = -2 gives Anti-Stoke lines
Even at room temperature, molecules with different J values are present. Hence good
number of stokes as well as anti-stoke lines of comparable intensity are observed.
The wave number of the rotational lines
Raman 0 B J 2 J 3 BJ J 1
0 4B J 3 / 2
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The rotational Raman shift
4 B J 3 / 2
6 B,10 B,14 B,18 B,...
Thus pure rotational Raman spectrum consists of series of equidistance lines.
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4
3
2
1
0
ks
4B 4B 6B 6B 4B 4B
4B
υ(cm-1)→
υ0
4B 4B 6B 6B 4B 4B
Stokes Line Anti-Stoke Line
υ
zi
Important Facts:
1.) Raman effect is a tool for determining structure of diatomic and polyatomic molecules
and their bond length and force constant.
2.) Besides the molecule like HCl, the homonuclear molecules like H2, N2, O2, etc also
shows Raman spectra, although they do not show infra res spectra.
3.) Rule of Mutual Exclusion:- if a molecule has a center of symmetry then Raman active
vibrations are infra-red inactive and vice versa.
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There is no centre of symmetry then some (but not necessary all) vibration may be both
Raman and infra-red active.
Mode of vibration of CO2 Raman Infra-red
1: symmetry stretch Active Inactive
2: bend Inactive Active
3: Asymmetric stretch Inactive Active
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4.) Raman shift for stokes line: Δυ = υo - υs
Raman shift for Anti-stokes line: Δυ = υa – υo
5.) Laser light: Use of laser light gives very narrow, highly monochromatic, coherent beam
which can be focused to a very small sample laser can also be extremely powerful (high
intensity), this reduces the measurement time.
Example 1: A substance shows a Raman line at 4567 Ǻ, when exciting line 4358 Ǻ is
used. Find the position of stokes an anti-stoke line for the same substance when the
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exciting lien 4047 Ǻ used.
Solution:
vo 22946 cm 1 v R 21896 cm 1
Raman shift: v v o v R = 1050 cm-1
v does not depend upon the incident frequency
1
v0' 8
24710cm1
4047 10 cm
Thus, the wave number of stokes & anti-stokes lines are
zi
= v'o v = (24710 ± 1050) cm-1
= 23660 cm-1 amd 25760 cm-1
or λstoke = 4226 Ǻ
λanti-stoke = 3882 Ǻ
fi
Head office Branch office
fiziks, [Link]. 40 D, G.F, Jia Sarai, Anand Institute of Mathematics,
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