Subject Chemistry

Paper No and Title 8/ Physical Spectroscopy

Module No and Title 24/ Rayleigh and Raman scattering. Stokes and anti-Stokes
lines. Rotational Raman spectroscopy. Polarizability
ellipsoid. Selection rules.
Module Tag CHE_P8_M24

TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction

3. The Classical Theory of the Raman Effect (Molecular Polarizability)

4. The Quantum Theory of the Raman Effect

5. Pure Rotational Raman Spectra

6. Summary

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE NO. : 24 (RAYLEIGH AND RAMAN SCATTERING.
STOKES AND ANTI-STOKES LINES. ROTATIONAL RAMAN
SPECTROSCOPY. POLARIZABILITY ELLIPSOID.
SELECTION RULES)
 1. Learning Outcomes
After going through this module, you should be able to:

(a) Explain the classical theory of the Raman effect and polarizability
(b) Explain the quantum theory of the Raman effect
(c) Understand the rotational Raman spectra

2. Introduction
Raman spectroscopy is another form of spectroscopy, which is used for structure determination.
Unlike the other techniques, it is based on the scattering of light. When a beam of monochromatic
radiation passes through a liquid or gas, it might be transmitted, absorbed or scattered. In the case
of light scattering, nearly all of the scattered light is observed at the same frequency as the
incident light (a phenomenon known as elastic or Rayleigh scattering). However, the great Indian
physicist Sir C.V. Raman observed in 1928 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. The Raman Effect comprises a very small fraction, about 1 in 107, of the
incident photons. A powerful laser source in the visible or UV region is used as the light source.

Figure 1 shows Rayleigh and Raman scattering. The lines at lower frequency than the incident
radiation are known as Stokes lines, and those at higher frequency are called anti-Stokes lines.

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE NO. : 24 (RAYLEIGH AND RAMAN SCATTERING.
STOKES AND ANTI-STOKES LINES. ROTATIONAL RAMAN
SPECTROSCOPY. POLARIZABILITY ELLIPSOID.
SELECTION RULES)
 Figure 1: Rayleigh and Raman scattering

Unlike the other techniques, the molecular property that must change for a rotation or vibration to
be Raman active is the molecular polarizability, which is a measure of the ease with which the
electron cloud in a molecule can be distorted. This rule should be contrasted with that for IR and
microwave activity, which states that the molecular motion must produce a change in the electric
dipole of the molecule. Thus, Raman spectroscopy can be used on species with no dipole
moment, e.g. H2, Cl2, etc., thus complementing microwave spectroscopy.

3. The Classical Theory of the Raman Effect (Molecular Polarizability)

When a static field is applied on a molecule, a polarization of charge takes place, the positively
charged nuclei getting attracted to the negative pole of the field, and the electronic cloud to the
positive pole. A dipole is induced in the molecule, even if it has no dipole moment initially, and
the molecule is said to be polarized. The induced electric dipole moment, µind, depends on both
the magnitude of the applied field, E, and the ease with which the electron cloud of the molecule
can be distorted.

Thus,

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE NO. : 24 (RAYLEIGH AND RAMAN SCATTERING.
STOKES AND ANTI-STOKES LINES. ROTATIONAL RAMAN
SPECTROSCOPY. POLARIZABILITY ELLIPSOID.
SELECTION RULES)
 µind = αE (1)

where α is the polarizability of the molecule.

The polarizability is anisotropic, which means that the induced dipole moment is not the same in
all directions. The polarizability is greater along the bond axis than across it since it is difficult to
polarize in a direction perpendicular to the internuclear axis.

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 centre of
the molecule is proportional to 1/√αi, where αi 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 (it is the minor axis of the ellipsoid).

Since the polarizability of a diatomic molecule is the same in all directions at right angles to the
bond axis, the ellipsoid has a circular cross section in these directions (Fig. 2).

(a) (b)

(c) (d)

Figure 2: Polarizability ellipsoid of hydrogen molecule

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 = E0sin2πνt, (2)

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE NO. : 24 (RAYLEIGH AND RAMAN SCATTERING.
STOKES AND ANTI-STOKES LINES. ROTATIONAL RAMAN
SPECTROSCOPY. POLARIZABILITY ELLIPSOID.
SELECTION RULES)
 A time-dependent dipole moment is, therefore, induced in
the molecule:

µind = αE = αE0sin2πνt (3)

where E0 is the strength of the applied field.

According to electromagnetic theory, an oscillating dipole emits radiation whose frequency is the
same as its oscillation frequency. Equation (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 the vibrational or rotational oscillation. The oscillating dipole has frequency ν ± νvib 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, we have the selection 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 the magnitude or direction of the polarizability ellipsoid.

4. The Quantum Theory of the 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 collisions result in energy exchange
between the photon and the molecule, while elastic collisions result in no energy exchange at all.
If the molecule gains energy ΔE from the photon, the photon will be scattered with energy (hv -
ΔE) and with frequency (v - ΔE/h). If, however, the molecule loses energy ΔE to the incident
radiation, the scattered radiation will have a frequency of (v + ΔE/h).

Radiation scattered with a frequency lower than that of the incident radiation is known as Stokes
radiation, while that of a higher frequency is anti-Stokes radiation. Rayleigh scattering is the
situation where the scattered radiation has the same frequency as the incident radiation (see Fig.
1).

5. Pure Rotational Raman Spectra

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE NO. : 24 (RAYLEIGH AND RAMAN SCATTERING.
STOKES AND ANTI-STOKES LINES. ROTATIONAL RAMAN
SPECTROSCOPY. POLARIZABILITY ELLIPSOID.
SELECTION RULES)
 We restrict ourselves to linear molecules. From Figure 2, it is
clear that the polarizability ellipsoid of a diatomic molecule
changes in appearance when the molecule rotates, and for the first time we are able to get
rotational constants for homonuclear diatomic molecules like H2 and N2. However, symmetrical
molecules like CCl4 and SF6 have spherical polarizability ellipsoids and they are neither
microwave active nor Raman active, since their polarizability ellipsoids neither change size nor
shape during rotations.

It is also clear from Figure 2 that the polarizability ellipsoid of a linear molecule presents the
same appearance twice during a complete rotation.

The selection rule for rotational transitions for Raman spectroscopy is:

DJ = 0, ± 2 (4)

The DJ = 0 selection rule refers to Rayleigh transitions, DJ = -2 to emissions, and we may

ignore both of these in case of absorptions (Stokes lines).

The rotational energy levels of linear molecules are given by:

~
F ( J ) = B J ( J + 1) J = 0, 1, 2, … (5)

Here, we have not considered centrifugal distortion since the accuracy of Raman spectroscopy is
not too high to warrant its inclusion.

The energy difference between the excited and ground state is given by

De = F ( J + 2) - F ( J )
~ ~
= B ( J + 2)( J + 2 + 1) - B J ( J + 1) (6)
~
= B ( 4 J + 6)

where J is the rotational quantum number of the lower state (= 0, 1, 2, …). The lines resulting
from these energy changes are referred to as the S branch line since we have considered only ΔJ
= +2.

Thus, if the molecule gains rotational energy from the photon during collision, we have a series of
S branch lines on the low wavenumber side of the exciting line (Stokes lines), while if the
molecule loses energy to the photon, the S branch lines appear on the high wavenumber side
(anti-Stokes lines). The wave numbers of the corresponding spectral lines are thus given by:

~
n~s = n~ex ± B (4 J + 6) (7)

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE NO. : 24 (RAYLEIGH AND RAMAN SCATTERING.
STOKES AND ANTI-STOKES LINES. ROTATIONAL RAMAN
SPECTROSCOPY. POLARIZABILITY ELLIPSOID.
SELECTION RULES)
 where the minus refers to the Stokes lines and the plus to the
anti-Stokes lines.

The allowed transitions and the Raman spectrum arising is shown in Figure 3. The spacing
~ ~
between adjacent lines is 4 B and the first line to each side of the exciting line is at 6 B . Thus,
~
the Raman spectra yield values of B and hence the moments of inertia and bond lengths for
small molecules. Raman spectroscopy is supplementary to microwave and infrared 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 3: Pure rotational Raman transitions and spectrum

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE NO. : 24 (RAYLEIGH AND RAMAN SCATTERING.
STOKES AND ANTI-STOKES LINES. ROTATIONAL RAMAN
SPECTROSCOPY. POLARIZABILITY ELLIPSOID.
SELECTION RULES)
 ---

Example 1

-1
The wavenumber of the incident radiation is 20000 cm . What is the wavenumber of the
scattered Stokes radiation for the J = 0 → 2 transition of 14N2 . The equilibrium bond length is 110
pm.

Solution

-3 23
For a homonuclear diatomic molecule, the reduced mass µ = 14.0067×10 /2/6.02214×10 =
-26
1.16293×10 kg.

The moment of inertia I = mr 2 = 1.16293 ´ 10 -26 ´ (110 ´ 10 -12 ) 2 = 1.41 ´ 10 -46 kg m2

The rotational constant

~
B = h / 8p 2 Ic = 6.626 ´ 10 -34 / 8 / 3.1416 2 / 1.41 ´ 10 -46 / 2.998 ´ 1010 = 1.985 cm-1
~
The Stokes lines occur towards the low wavenumber side and the first transition is at 6 B .
-1
Therefore, the line will appear at 20000-6×1.985 = 19988 cm .

6. Summary
· Raman spectroscopy is based on the scattering of light.
· Most of the scattered radiation has the same frequency as the incident radiation and this is
called Rayleigh scattering.
· A small part has discrete frequencies at the lower (Stokes lines) and higher (anti-Stokes)
sides.
· For a species to be Raman active, the vibration or rotation must cause some change in the
polarizability of the molecule.
· A change in polarizability is reflected by a change in either the magnitude or the
direction of the polarizability ellipsoid.
· Raman spectroscopy can give information about species with no dipole moments, hence
complementing microwave and IR spectroscopy.

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE NO. : 24 (RAYLEIGH AND RAMAN SCATTERING.
STOKES AND ANTI-STOKES LINES. ROTATIONAL RAMAN
SPECTROSCOPY. POLARIZABILITY ELLIPSOID.
SELECTION RULES)