LESSON FOUR RAMAN SPECTROSCOPY

4.1 Introduction

When a beam of monochromatic radiation is passed through a liquid of gaseous substance, it

might be transmitted, absorbed or scattered. When molecules scatter light, nearly all of the
scattered light is observed to be of the same frequency as the incident light (a phenomenon
known as elastic or Rayleigh scattering). However, longer exposures have shown that some of
the scattered light also has discrete frequencies above and below the incident frequency. This
phenomenon is known as inelastic or Raman Scattering (after the indian physicist C.V.
Raman1928). The Raman Effect comprises a very small fraction, about 1 in 10 7, of the incident
photons.
In order to be Raman active a molecular rotation or vibration must cause some change in a
component of the molecular polarizability. A change in polarizability is reflected by a change
in either the magnitude or the direction of the polarizability ellipsoid. (This rule should be
contrasted with that for IR and microwave activity, which is that the molecular motion must
produce a change in the electric dipole of the molecule). Raman spectroscopy applies to
species with no dipole moment, e.g. H2, Cl2 etc, thus complementing microwave
spectroscopy.

4.2 Lessons Learning Outcomes

By the end of this lesson, you will be able to:
(a) Explain how stokes, anti-stokes and rayleigh lines arises
(b) Derive and use formula for Raman spectroscopy
(c)Explain the Quantum and classical theories theory of Raman effect
(d) Explain Rotational Raman spectra
(e) Explain vibrational Raman spectra

4.2.1 The Quantum Theory of Raman Effect

According to the Quantum Theory, radiation of frequency v can be pictured as a stream of
particles (called photons) each having energy hv. These photons are imagined to undergo
either inelastic or elastic collisions with molecules. Inelastic collision results energy
exchange between a photon and a molecule while elastic collision results in no energy
exchange at all. If the molecule gains energy E, from the photon, the photon will be
scattered with energy (hv - E) and with frequency (v - E/h). If however, a molecule loses
energy E to the incident radiation, the scattered radiation will have a frequency of (v +
E/h).
Radiation scattered with a frequency lower than that of the incident radiation is known as
Stoke’s radiation, while that of a high frequency is anti-Stoke’s radiation. Rayleigh
scattering is the situation whereby the scattered radiation has the same frequency as the
incident radiation (see Fig 10).

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Figure 10 Energy level diagram showing the states involved in Raman signal. The line thickness is roughly
proportional to the signal strength from the different transitions. Source: http://en.wikipedia.org/wiki/Raman_
spectroscopy

E-tivity -3.2.1 The Quantum Theory of Raman Effect.

Numbering, pacing and 2.2.1

sequencing
Title The Quantum Theory of Raman Effect.
Purpose The purpose of this e-tivity is to enable you to describe The
Quantum Theory of Raman Effect
Brief summary of overall task Read the materials on these links
https://www.youtube.com/watch?v=y7xAVzReba0&t=
230s&ab_channel=PhysicalChemistry

Spark

Individua task a) Derive the equation of stokes, stokes nad antistokes

lines

Interaction begins 1. Post two themes that are in Raman spectra

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 2. Provide positive and constructive feedback on the
team learners ‘views and ideas. Do this on the
discussion forum 1.2.4
E-moderator interventions 1. Ensure that learners are focused on the contents and
context of discussion.
2. Stimulate further learning and generation of new
ideas.
3. Provide feedback on the learning progress.
4. Round-up the e-tivity
Schedule and time This task should take two hours
Next The Classical Theory of Raman Effect (Molecular
Polarizability)

4.3.1 The Classical Theory of Raman Effect (Molecular Polarizability)

When a molecule is put in a static electric field it suffers some charge distortion, the
positively charged nuclei being attracted towards the negative pole of the field while the
electronic cloud is attracted to the positive pole. Such a molecule with separation of charge
centres is said to be polarized and possesses an induced electric dipole moment, . The
size of the induced dipole, , depends on both the magnitude of the applied field, E, and
the ease with which the molecule can be distorted.
Thus,
 = E (4.1)
where  is the polarizability of the molecule
The polarizability is anisotripic. This means that the electrons forming the bond are more
easily displaced by the electric field applied along the bond axis than one across this bond
axis. (Fields in other directions induce intermediate dipole moments).

The polarizability in various directions is conveniently represented by drawing a

polarizability ellipsoid. The ellipsoid is a three dimensional surface whose distance from the
electrical center of the molecule (i.e. centre of gravity) is proportional to 1/ri, where i is
the polarizability along the line joining point i on the ellipsoid with the electrical centre.
Thus, where the polarizability is greatest the axis of the ellipsoid is least.

Since the polarizability of a diatomic molecule is the same for all directions at right angles
to the bond axis, the ellipsoid has a circular cross section in this direction. When a sample
of diatomic molecules is subjected to a beam of radiation of frequency v the electric field
experienced by each molecule varies as follows:

E = E0sin2νt, (4.2)
A time-dependent dipole moment is, therefore, induced in the molecule:
 = E = E0sin2νt.
(4.3)
E0 is the strength of the applied field.

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 According to the electromagnetic theory, an oscillating dipole emits radiation whose
frequency is the same as its oscillation frequency. Equation 4.3 is therefore, the classical
explanation of Rayleigh scattering.

If in addition, the molecule undergoes some internal motion, such as a vibration or a rotation,
which changes the polarizability periodically then the oscillating dipole will have
superimposed upon it the vibrational or rotational oscillation. The oscillating dipole has
frequency v  vib as well as the exciting frequency v. It should be noted that if the vibration
or rotation does not change the polarizability of the molecule the dipole oscillates only at the
frequency of the incident radiation. Thus, there is the Rule:
“In order to be Raman active a molecular rotation or vibration must cause some change in
a component of the molecular polarizability”. A change in polarizability is reflected by a
change in either magnitude or direction of the polarizability ellipsoid. (The structure of
polarizability ellipsoids is dealt with elsewhere in the current unit)

4.4.1 Pure Rotational Raman Spectra

We restrict ourselves to linear molecules. The rotational energy levels of linear molecules
are given by:
 J  BJ ( J  1) cm 1 , ( J  0 , 1 , 2 , ... ) (4.4)
where the centrifugal distortion constant is not considered .
The formal selection rule for transitions between these energy levels for Raman
spectroscopy (only) is:
J  0 , or  2 (4.5)
In practice ΔJ is defined as follows
J  J upper  J lower
and consequently ΔJ =-2 may be ignored since for pure rotational states Jupper>Jlower. J =
0 is trivial since this represents no change in molecular energy and hence gives Rayleigh
Scattering only.
   J  2  J    J  J
 B ( J  2)( J  2  1)  BJ ( J  1)
 B ( 4 J  6) cm 1 , ( J  0 , 1 , 2 , ...) (4.6)
where J is the rotational quantum number in the lower state. The lines resulting from these
energy changes can be referred to as S branch line since we consider only ΔJ = +2.
Thus, if the molecule gains rotational energy from the photon during collision we have a
series of S branch lines to the low wave number side of the exciting line (Stoke’s lines ),
while if the molecule loses energy to the photon the S branch lines appear on the high wave
number side (anti-Stoke’s lines ). The wave numbers of the corresponding spectral lines are
given by:
 s   ex  B(4 J  6) cm 1 , (4.7)

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 where the minus refers to the Stoke’s lines and the plus refers to the anti-Stoke’s lines.
The allowed transitions and the Raman spectrum arising is shown below. The Raman spectra
yield values of B and hence the moments of inertia and bond lengths for small molecules.
Raman spectroscopy is supplementary to Rotational and IR methods. It is a method for
obtaining molecular parameters of homonuclear diatomic molecules which are IR and
microwave inactive due to the absence of permanent dipole moments in the molecules.

Figure 11: Pure rotational Raman transitions and spectrum

4.5 Structure of Polarizability Ellipsoids

In this section we try to show pictorially the polarizability ellipsoids as changed by various
vibrational modes of the water molecule. Note that the ellipsoids are only two-
dimensional.

Figure 12: Vibrational modes of water

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4.6 Vibrational Raman Spectra
For every vibrational mode one writes:
   e (  1 / 2)   e  e (  1 / 2) 2 cm 1 (  0 ,1 , ...) (4.06.01)

where  e is the equilibrium vibrational frequency in reciprocal centimeters and  e is the

anharmonicity constant. The selection rule is:
 = 0, 1, 2, … (4.06.02)
which are the same for Raman as for IR spectroscopy . The probability of  = 2, 3,
… decreases rapidly and may be ignored. Application of the selection rules to equation
(4.06.01) yields :

  0   1
 fundamental   e (1  2  e ) cm 1
(4.06.03)

  0   2
 overtone  2 e (1  3 e ) cm 1 (4.06.04)

  1   2
 hotband   e (1  4  e ) cm 1 (4.06.05)
We restrict ourselves to fundamental transitions only. We would expect Raman lines to
appear at distances from the exciting line corresponding to each active fundamental
vibration. Therefore,
 fundamental   ex   fundamental cm 1 (4.06.06)
The vibrational Raman spectrum of a molecule will then show a series of reasonably intense
lines. The minus represents the situation where the molecule has gained energy, (Stoke’s
lines), and the plus indicates when the molecule has lost energy, (anti-Stoke’s lines). The
anti-Stoke’s lines are weak since few molecules will have gained energy.

4.7 The Rule of Mutual Exclusion

If a molecule has a center of symmetry, then Raman active vibrations are IR inactive, and IR
active modes are Raman inactive. If there is no center of symmetry then some (but not
necessarily all) vibrations will be both Raman and IR active. Hence, if some vibrations are
observed to give coincident Raman and IR absorptions it is certain that the species has no center
of symmetry.

4.8 Summary

For a species to be Raman active the vibration or rotation must cause some change in the
polarizability of the molecule. Raman spectroscopy may give information about species with

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no dipole moments hence complementing that from microwave and IR spectroscopy.

4.9 Terminal Questions

Q1. (a) Explain the following terms as used in Raman spectroscopy:

(i) Stoke’s radiation
(ii) anti-Stoke’s radiation
(iii) Rayleigh scattering

(b) The rotational energy levels of linear molecules are given as:

 J  BJ ( J  1) cm 1 , ( J  0,1,2, ...) .
Show that for pure rotational Raman spectra, one has:

 J  B(4 J  6) cm 1 , ( J  0,1,2,...)
Q2. Molecules, according to their shapes, are classified on the basis of their relative values of
their moments of inertia: IA, IB and IC. Name the classifications, giving an example of each.
Q3. Using the Quantum theory of Raman Effect, explain how the Stoke’s, Rayleigh and anti-
Stoke’s lines are produced.
Q4. Discuss the Classical theory of Raman Effect.
Q5. State the rule of ‘mutual exclusion’ in Raman spectroscopy.
Q6. Explain the mode of interaction between matter and radiation in Raman spectroscopy.

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