BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 16
30 Nov 2022
AY 2022-23, Sem-I
Raman and Vibrational Spectroscopy
BITS Pilani, Pilani Campus
Lecture 14 - Summary

Spectroscopy
• Rotational Spectroscopy
• General conditions for observing rotational
spectra – Energy and Intensity of transitions
• Selection rules

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Lecture 15 - Summary
• Hence, population at any level, PJ can be expressed as,
PJ = P0.gJ.e(-EJ /kT)
PJ  ( hBJ ( J 1) /( kT ))
or,  (2 J  1)e
P0
• The distribution passes
through a maximum at a
certain value of J, which can
be obtained at 1/ 2
 kT  1
J  J max    
dPJ/dJ = 0  2hB  2

Population is going govern

intensity of spectral transitions
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Lecture 15 - Summary

Work out: For temperatures of 25 °C and

1000 °C, calculate the ratio of molecules
in a typical excited rotational level (J =4)
to that in the lowest energy level,
assuming the excited level is 30 cm-1
above the lowest energy level.
{0.11 of Text Book} 4 BITS Pilani, Pilani
Lecture 15 - Summary
Transition dipole moment :  final  initial d
Square of this value determines intensity. If transition
dipole moment is 0 then no transition takes place.
Selection Rules
Gross selection Rule: The molecule must be polar.
For polar molecules oscillating electric dipole is generated
by rotation.
Specific selection Rule: ∆J = ±1
This is based on conservation of angular momentum
Therefore for a rigid rotor, we can write
∆E = EJ+1-EJ = 2hB(J+1) or, nJ = 2B(J+1)
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Raman Spectroscopy

6
Scattering phenomenon
Type – I: Elastic scattering

𝝂i 𝝂i Detector
Light
(1)
source

𝝂i Condition-1: Without any sample

Condition-2: With sample

Type – I scattering is Rayleigh scattering

Detector
(2)
J” State of the
system remains
J’ unchanged
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Scattering phenomenon
Type – II: Inelastic scattering

𝝂i 𝝂i Detector
Light
(1)
source

Type – II scattering is Raman scattering

𝝂i - 𝛥 𝝂 𝝂i + 𝛥 𝝂
Detector
J’’ J’’
Energy

(2)

J’ J’
J J
Case-I Case-II
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Raman Spectroscopy
Case-I Case-II
𝝂i - 𝛥 𝝂 𝝂i + 𝛥 𝝂
Case-I: Molecule J’’ J’’ Case-II: Molecule
Energy
gains energy, 𝛥E; release energy, 𝛥E;
State changes J’ J’ State changes from
from J to J’. J” to J’.
J J

Stokes’ radiation Anti-Stokes’ radiation

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Raman Spectroscopy - explanation
+ ve -
ve
This separation of
charge centers
- ve + ve causes an induced
electric dipole
moment
Molecule is polarized

Polarization leads to dipole moment in the molecule –

induced dipole moment
Induced dipole:  = a E; E = applied field
a is a parameter – the ease with which a molecule can
be distorted - POLARIZABILITY
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Raman Spectroscopy – Selection rule
Gross Selection Rule
Some internal motion of the molecule, such as, rotation
and/or vibration must change the polarizability, i.e., ≠ 0

q represents the coordinate in terms of the

internal motion
If molecular rotation/vibration causes some change in molecular
polarizability then those rotation/vibration must be Raman Active

All diatomic molecules are Raman active.

Spherical rotors such as CH4 , SF6 are inactive.
Conditions imposed on rotation model we have used:
Molecules must be non-rigid and hence polarizable
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Pure rotational Raman Spectroscopy
Polarizability: Bonds must be non-rigid.
For practical purposes (limited resolution) we may not obtain any
information about the distortion of the molecules.
Thus, we can start with EJ = BJ(J+1) cm-1, J = 0,1,2,….

Specific Selection Rule (For linear molecules)

ΔJ = 0 or ±2 only (Rotational Raman)
ΔJ = 0 → Trivial transition, represents Rayleigh scattering
E = hB[(J+2)(J+3) – J(J+1)] = 2hB(2J + 3) in energy units
= B[(J+2)(J+3) – J(J+1)] = 2B(2J + 3) in frequency units

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Pure rotational Raman Spectroscopy

Stokes lines at 6B, 10B, 14B,… lower than incident and

Anti-Stokes at 6B, 10B, 14B,… higher than incident frequency.
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Rotational Raman spectrum of CO2
Applications
Homonuclear
diatomics:
• H2, O2, N2:
Rotationally inactive
• Active in rotational
Raman
• Raman spectroscopy
provide information
about the structure

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Application of MW spectroscopy: Mapping molecular cloud in interstellar medium

Microwave and millimeter wave astronomy: Microwave identification of molecules

Microwave spectrum of the Orion nebula

Taurus molecular cloud observed at

115 GHz. 12CO emission (J = 1 – 0)
Not in Syllabus
{Source: Astrochemistry from Astronomy to
Astrobiology, by Andrew M. Shaw, Wiley}
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Line of sight through three Giant Molecular
Clouds to the Hubble Space Telescope
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Application of Raman spectroscopy: Single molecule detection

A methodology based on surface-enhanced Raman

scattering (SERS)

Rhodamine 6G

Not in Syllabus
Direct comparison of laser-induced fluorescence
and SERS of a single R6G molecule.
Ref: S. Nie et al., Science, 1997, Vol. 275, PP. 1102-1106, http://www.sciencemag.org 16 BITS Pilani, Pilani
Vibrational Spectroscopy

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Vibrational spectroscopy
Diatomic molecule: A-B
k is the force constant with unit as N m-1
Using the harmonic approximation:

In terms of wave number:

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Vibrational Levels

Depth of the potential

energy well indicates the
strength of the bond (in
terms of force constant, k)

At v=0, Zero Point Energy

is ½ hn
Vibrational energy levels
are equispaced at hn

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Vibrational spectroscopy
Gross Selection Rule:
The electric dipole moment of the molecule must change
during the vibration. This can be expressed as
Where  = dipole moment, q = internal coordinate
in terms of the vibrational motion
Molecule need not have permanent dipole in it
Thus, homonuclear diatomic molecules such as H2 are
vibrationally inactive (as also are rotationally inactive)
Specific selection rule:
v = 
For any vibrational transition, ∆E = Ev+1 –Ev = hcῡ
Generally, most important transition from v = 0 to v = 1.
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Vibrational spectroscopy
Vibrational transitions occur at frequencies of 1013 to 1014Hz,
thus it is also called as infrared (IR) spectroscopy.

Ex.1 A single oxygen atom is attached to a smooth metal surface. The

atom vibrates at a frequency of 1.80 X 1013 s-1. Calculate its total
energy for n = 0, 1, and 2 quantum no. states.

Ans: E (n=0) = 5.963 X 10-21 J; E (n=1) = 1.789 X 10-20 J; and

E (n=2) = 2.982 X 10-20 J

Ex. 2: Calculate the wavelength of light necessary to excite a

harmonic oscillator from one energy state to the adjacent state in the
previous example. Ans: 16.66 m

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Anharmonicity
Harmonic Approximation: Bond
cannot break
Anharmonicity Anharmonic
Harmonic

xe is anharmonicity constant
Plot is called a Morse Curve
Other observations:
• Dissociation of bond can be
explained
• The initial absorption appear v = 1
known as fundamental absorption Overtones
• Additional weak absorption lines or
overtones appear corresponding to Morse Curve
v = 2,3,..

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Vibrational Spectroscopy of Polyatomic Molecules

Normal Modes:
Description of vibration is most convenient and simple in
terms of normal modes.
Normal mode – Collective, independent, synchronous
motion of group of atoms, that may be excited without
exciting any other mode.
Each normal mode may be approximated as a harmonic
oscillator with a characteristic frequency and an effective
mass.
Any arbitrary displacement may be expressed as a
superposition of the normal modes.

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Discussed topics……

Vibrational Spectroscopy
• Raman spectroscopy
• Rotational Raman spectroscopy
• Vibrational energy levels; Gross and Specific selection
rules;

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