Rotational Spectroscopy Part 1

Ankita Ojha
Department of Chemistry
Maharaja College
Arrah
Introduction
 Rotational spectroscopy is concerned with the measurement of the energies
of transitions between quantized rotational states of molecules in the gas
phase.
 It is a uniquely precise tool for the determination of molecular structure in

gas phase molecules.
 Pure rotational transitions in a molecule can be induced by radiation in the

far infrared and microwave regions of the spectrum.
 Two requirements that restrict the microwave studies are : 1) the spectrum
must be obtained in the gaseous state. 2) the molecule must have permanent
dipole moment in the ground state in order to absorb microwave radiation.
 Electric dipole, p= q.d where q is the charge and d is the
distance between the charges. (HCl molecule)
+q -q
+q -q
d
p
p
Most of the heteronuclear molecules such as HCl, H2O, NH3 etc.

possess dipole moment and hence show rotational spectra.
Molecules can interact with electromagnetic radiation, absorbing or

emitting a photon of frequency ω, if they possess an electric dipole moment
p, oscillating at the same frequency
Gross Selection Rule:
A molecule has a rotational spectrum only if it has a permanent dipole moment.
Rotating molecules
- + - +
Dipole moment, p
+ - + -
Homonuclear molecules (e.g. O2, H2, Cl2, Br2…. do not have a
permanent dipole moment and hence they do not have a microwave
spectrum
Rotating Systems
Linear velocity= distance/time Angular velocity, ω= radians/time
m v v= ω x r
𝑰= 𝒎𝒊 𝒓𝟐𝒊 Moment of inertia, I = mr2
𝒊
ri stands for the A molecule can have three different
distance perpendicualr O r moments of inertia IA, IB and IC
to the axis of rotation.
about orthogonal axes a, b and c.
IA
R IC
IB
ri
Rigid Diatomic Rotors
r0
C stands for centre of gravity
C
m1 m2
𝒎𝟏 𝒎𝟐 𝟐
𝑰= 𝒓𝟎
r1 r2 𝒎𝟏 + 𝒎𝟐
𝑰 = 𝝁𝒓𝟐𝒐
Where μ stands for reduced mass or the effective mass of the

molecule and is given by the equation The rotations of a diatomic
molecule can be modeled as
𝒎𝟏 𝒎𝟐 a rigid rotor. This rigid rotor
𝝁= model has two masses
𝒎𝟏 + 𝒎𝟐 attached to each other with
a fixed distance between
the two masses.
Classification of molecular rotors
• The particular pattern of energy levels (and, hence, of transitions in the rotational
spectrum) for a molecule is determined by its symmetry. A convenient way to look
at the molecules is to divide them into four different classes, based on the symmetry
of their structure.
• IA denotes the axis A which is the axis of rotation for highest order. The general
convention, used in this article, is to define the axes such that with axis 𝐼𝐴 ≤ 𝐼𝐵 ≤
𝐼𝐶 with axis A, corresponding to the smallest moment of inertia.
• The particular pattern of energy levels (and, hence, of transitions in the rotational
spectrum) for a molecule is determined by its symmetry. A convenient way to look
at the molecules is to divide them into four different classes, based on the symmetry
of their structure.
Spherical tops (spherical rotors): All three
moments of inertia are equal to each other
i.e. 𝐼𝐴 = 𝐼𝐵 = 𝐼𝐶 . Molecules with tetrahedral
or octahedral symmetry mostly come in this
zone eg. CH4, CCl4, SF6.
Linear molecules: For a linear molecule the

moments of inertia are related by 𝐼𝐴 ≪ 𝐼𝐵 =
𝐼𝐶 . The value of 𝐼𝐴 mostly stands zero in this
case. Molecules with C∞h and D∞h symmetry
comes in the category. Eg. Carbondioxide,
HCN, Acetylene, CO etc.
Symmetric tops (symmetric rotors) A symmetric top is a molecule in which
two moments of inertia are the same, i.e. 𝐼𝐴 = 𝐼𝐵 𝑜𝑟 𝐼𝐵 = 𝐼𝐶 . By definition
a symmetric top must have a 3-fold or higher order rotation axis. They are
further categorized into two types : Prolate ( 𝐼𝐴 < 𝐼𝐵 = 𝐼𝐶 ) for the
molecules such as Propyne and chloromethane and Oblate (𝐼𝐴 > 𝐼𝐵 = 𝐼𝐶 )
for the molecules such as benzene and ammonia.
Oblate symmetry in Ammonia Prolate symmetry in Propyne

Degrees of Freedom
Translational: It entails the movement of the entire molecule’s center of mass. This
movement can be completely described by three orthogonal vectors and thus contains 3
degrees of freedom.
Rotational: The rotations around the center of mass of the molecule and they are also
described by three orthogonal vectors i.e. it contains only 3 degrees of freedom.
However, in the case of a linear molecule only two degrees of freedom are present due to
the rotation along the bonds in the molecule having a negligible inertia.
Vibrational: 3N – 6 degrees of vibrational freedom for a nonlinear molecule and 3N – 5
for a linear molecule. These vibrations include bending, stretching, wagging and many
other aptly named internal movements of a molecule. These various vibrations arise
due to the numerous combinations of different stretches, contractions, and bends that
can occur between the bonds of atoms in the molecule.
The quantum expression for angular momentum in a rigid rotor is given as:
1 ℎ
𝑃𝐽 = [𝐽 𝐽 + 1 ]2
2𝜋
According to Schrödinger equation for a rigid rotor :
ℎ2
𝐸𝐽 = 2 𝐽(𝐽 + 1)
8𝜋 𝐼
Where J stands for rotational energy level and its value is always an integer 0,1,2,3,4….
Selection Rules of Rotational Spectroscopy
There are three rules for rotational spectra out of which two
holds very firm role:
1. The molecule must have a permanent dipole moment i.e.
𝜇 ≠ 0.
2. ∆𝐽 = ±1
3. ∆𝑀𝐽 = 0, ±1 this rule only holds for the cases when the
molecules is in electric or magnetic field.
Structure of rotational spectra
Spherical top molecules have no net dipole moment. A pure
rotational spectrum cannot be observed by absorption or
emission spectroscopy because there is no permanent dipole
moment whose rotation can be accelerated by the electric field
of an incident photon.
Under the rigid rotor model, the

rotational energy levels, F(J), of the
molecule can be expressed as,
𝐹 𝐽 = 𝐵𝐽(𝐽 + 1)
where B is the rotational constant of the
molecule and is related to the moment of
inertia of the molecule and J=0,1,2,3 and
the value of B is given by
ℎ2
𝐵= 2
8𝜋 𝐼 Image Source:
https://upload.wikimedia.org/wikipedia/commons/3/35/Rotational_spectrum_
example.png
For J= 0, F(0) = BJ(J+1) = B X 0 (1)= 0
For J=1, F(1) = BJ(J+1) = B X 1 (1+1)= 2B
For J=2, F(2) = BJ(J+1) = B X 2 (2+1)= 6B
For J=3, F(3)= BJ(J+1)= B X 3(3+1)= 12B
Therefore for transition from 0 1 the difference is 2B and for transition from 1 2
the energy difference is 4B. The above equation can be summarized as ΔF(J)= 2B(J+1)
and for J=0, ΔF(0)= 2B,
for J=1, ΔF(1)= 2B(J+1)=4B
J=2, ΔF(2)=2B(J+1)=6B
J=3, ΔF(3)=2B(J+1)= 8B
Hence it be summarized that for every transition while the energy of transition
increases the intensity of the transitions remains the same.
Rotational Raman spectroscopy
Molecular rotational transitions can also be observed by
Raman spectroscopy. Rotational transitions are Raman-
allowed for any molecule with an anisotropic polarizability
which includes all molecules except for spherical tops. This
means that rotational transitions of molecules with no
permanent dipole moment, which cannot be observed in
absorption or emission, can be observed, by scattering, in
Raman spectroscopy.
• Atkins, P. W.; de Paula, J. (2006). "Molecular Spectroscopy: Section: Pure
rotation spectra". Physical Chemistry (8th ed.). Oxford University Press.
pp. 431–469. ISBN 0198700725.
• Banwell, Colin N.; McCash, Elaine M. (1994). Fundamentals of Molecular
Spectroscopy (4th ed.). McGraw-Hill. ISBN 0-07-707976-0.
• Brown, John M.; Carrington, Alan (2003). Rotational spectroscopy of diatomic
molecule. Cambridge University Press. ISBN 0-521-53078-4.
• Hollas, M. J. (1996). Modern Spectroscopy (3rd ed.). Wiley. ISBN 0471965227.
The Content is in update….. Keep reading and wait for the further
update…..
Thank You
For any subject related query you can mail on
[email protected]

Rotational Spectroscopy Part 1

Uploaded by

Copyright:

Available Formats

Rotational Spectroscopy Part 1

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Rotational Spectroscopy Part 1

Uploaded by

Copyright:

Available Formats

Ankita Ojha

 It is a uniquely precise tool for the determination of molecular structure in

 Pure rotational transitions in a molecule can be induced by radiation in the

Most of the heteronuclear molecules such as HCl, H2O, NH3 etc.

Molecules can interact with electromagnetic radiation, absorbing or

Where μ stands for reduced mass or the effective mass of the

Linear molecules: For a linear molecule the

Oblate symmetry in Ammonia Prolate symmetry in Propyne

Under the rigid rotor model, the

For any subject related query you can mail on

You might also like