Atomic and Molecular Physics

Course Code: PHYS4009

Lecture Topic

Molecular Spectroscopy
By
Prof. Sunil Kumar Srivastava
Department of Physics
Mahatma Gandhi Central University
Motihari, Bihar-845401
Please see the video lecture at
https://www.youtube.com/watch?v=A2DQ_OxJ2Og
 Outline
Questions that comes in our mind ?
What is the term Spectroscopy?
What does light do to the molecules?
How can you produce a molecular spectrum?
What information does the molecular spectrum give?

What we achieve?
Understanding of:
- How light interacts with molecules
- Molecular Energy States
- How to use spectroscopy to quantitatively characterize molecule
- How to extract molecular information
 SPECTROSCOPY
Spectroscopy is the study of electromagnetic
spectra – the wavelength composition of light – due
to atomic and molecular interactions.
Interaction of radiation with matter

Reflection
Interaction of radiation with matter

Transmission
Interaction of radiation with matter

Absorption
Interaction of radiation with matter

Scattering
Interaction of radiation with matter

Photoluminescence
Spectroscopy is the study of matter (atom or molecule
or any substance ) by investigating light, sound, or
particles that are absorbed, emitted or scattered by
the matter under investigation with the help of
spectroscopic instruments
Light : Electromagnetic Radiation

E = E0 sin( kx − t )
B = B0 sin( kx − t )
2
k=  = 2

 Energy of Photon
c
E = h = h = hc~

h = 6.626 × 10−34 js c = 2.997 × 108 m/s

c
Wave frequency  =
 

1
Wavenumber ( cm ) ~ = −1

 (cm )
 Molecular Interaction with Light
E´ E´
Absorption ΔE = hν
hν
E E

E´ E´
Emission ΔE = hν
hν
E E

Scattering
hν hν
 Molecular Energy States

Electronic excited state

Energy

Electronic
transition
Vibrational state
(in visible
or UV)
Electronic ground state
Rotational
transition
Vibrational
(in microwave)
transition
(in infrared)
Rotational state

Internuclear Separation
Molecular Rotation in Diatomic Molecule

I =  R2
m1m2
=
m1 + m2

Permanent
dipole moment

The electric field of an electromagnetic wave

exerts a torque on a electric dipole
 Molecular Rotational Energy
1 2 1 2 1 2
E = I x + I y + I z
2 2 2
Angular momentum L = I

L2 J ( J + 1) 2
H =  =  J is Rotational Quantum Number
2I 2I
J ( J + 1) 2
E=
2I
𝐸 h
B=
_
𝐹 𝐽 = = 𝐵𝐽 𝐽 + 1 𝑐𝑚 1 For rigid rotor
ℎ𝑐
E _
8 2cI
F(J ) = = B J ( J + 1) − D J 2 ( J + 1)2 +  𝑐𝑚 1 For non-rigid rotor
hc
B is Rotational constant and D is centrifugal distortion constant
 Rotational Energy Level
Rigid Rotor Non-Rigid Rotor
_ _
𝐹 𝐽 = 𝐵𝐽 𝐽 + 1 𝑐𝑚 1 J 𝐹 𝐽 = 𝐵𝐽 𝐽 + 1 − 𝐷𝐽2 𝐽 + 1 2 … . 𝑐𝑚 1
6 J
6

5
5

4 Selection rule 4
J = 1
3 3
2 2
1 1
0 0
0 4B 8B 12B 0 4B 8B 12B

2B 6B 10B 2B 6B 10B
cm-1 → cm-1 →
Molecular Rotation in Polyatomic Molecule

The rotational spectra of molecules can be classified

according to their principal moments of inertia
c
I =  M i Ri2 b
i
a
Ic  Ib  I a

The particular pattern of energy levels and hence the

transitions in the rotational spectrum for a molecule is
determined by its symmetry. Based on the symmetry of
their structure, molecules are divided into four different
classes.
 Linear molecules

Ic = Ib  I a = 0
c
b

O C O
 Symmetric top
Ic  Ib = I a Ic = Ib  I a
Oblate Prolate

BF3 CH3Cl
Spherical top

Ic = Ib = I a

CH4

Asymmetric top

Ic  Ib  I a
H2O
 Books for Further Reading

1. Fundamentals of Molecular Spectroscopy by C. N. Banwell

(McGraw Hill)

2. Basic Atomic & Molecular Spectroscopy by J. M. Hollas

(Royal Society of Chemistry)

References:
http://hyperphysics.phy-astr.gsu.edu/hbase/index.html

Bruker application notes