Microwave Spectroscopy

 Microwave spectroscopy is also known as rotational

spectroscopy as it involves the rotation of the
molecules.
 Lies in the wavelength region: 1 cm-100 μm.
 Absorption of Electromagnetic Radiation - The Coupling Mechanism

An electromagnetic wave is an oscillating electrical field and interacts only with molecules
that can undergo a change in dipole moment.

The oscillating dipole can be provided by the rotation of a permanent dipole, for example
HCl. This type of interaction leads to microwave spectra

HCl

Fig. The rotation of a polar diatomic molecule, showing the fluctuation in the dipole moment measured in a particular
direction
 Incident electromagnetic waves can excite the rotational levels of
molecules provided they have an electric dipole moment.
 The electromagnetic field exerts a torque on the molecule.
 The spectra for rotational transitions of molecules is in
the microwave region of the electromagnetic spectrum.

 Absorption of microwave radiation causes heating due to increased molecular

rotational activity.
Homonuclear diatomic molecules (such as H2, O2, N2 ,
Cl2) – have zero dipole (non polar) - have zero change of
dipole during the rotation – hence NO interaction with
radiation - hence homonuclear diatomic molecules are
microwave inactive.
Heteronuclear diatomic molecules (such as HCl, HF, CO) –
have permanent dipole moment (polar compound) -
change of dipole occurs during the rotation – hence
interaction with radiation takes place – Therefore,
heteronuclear diatomic molecules are microwave active.
Note -Homonuclear molecules, however show rotational
Raman spectra (which is arises due to the polarisability of
the molecules.)
Differences between IR and microwave spectroscopy:
1. Absorption in microwave region is characteristic of a
molecule as a whole, where as spectrum in the IR region is
characteristic of the functional group present in the
molecule.
2. Resolution of the lines in the microwave spectrum is very
much greater than that of the IR spectrum.
3. In microwave spectroscopy, the substance must be in
gaseous state. On the other hand, in IR spectrum the
substance may be in solid, liquid or in gaseous state.
4. In microwave spectroscopy, the spectra observed are always
absorption spectra. But in the IR spectroscopy, the spectra
obtained may be absorption or emission spectra.
 Theory of Microwave spectroscopy
The moment of inertia for a diatomic (linear) rigid
rotator

m1 m2

Center of mass)

definition: r0 = r1 + r2 Balancing equation: m1r1 = m2r 2

Moment of inertia: I = m1r12 + m2r22

m1 m2
I =μr2 = reduced mass = r2
m1 + m2
ro = r1 + r2 ------------------------------------(1)
m1r1 = m2r 2 --------------------- (2)
I = m1r12 + m2r22 ------------------- (3)
= m2r2r1 + m1r1r2 ----------------(4)
I = r1r2 (m1 +m2) ----------------(5)
But from eq. 1 and 2
r2 = ro - r1
 m1r1 = m2r 2 = m2( ro - r1)
m1r1 = m2 ro - m2 r1
m1r1+ m2 r1 = m2 ro
r1(m1 + m2) = m2 ro

r1 = m2ro / (m1 + m2) and r2 = m1ro / (m1 + m2)

But I = m1r12 + m2r22
I = m1m22ro2 / (m1 + m2) 2+ m2 m12ro2 / (m1 + m2) 2 r22
I = m1m2ro2 (m1 + m2) / (m1 + m2) 2

I = μro2 ---------------------------------------------------(6)
Where μ = m1m2/ (m1 + m2); the reduced mass.

Thus the diatomic molecule is equivalent to a single point mass µ

at a fixed distance r from the axis of rotation. Such a system is
called a rigid rotator.
Rotational energy levels allowed to the rigid diatomic
molecule are given by the expression,
h2
E J  2 JJ  1 (Using Schrodinger
8π I
wave equation)

In this expression, h is Planck's constant and I is moment

of inertia.

The quantity J, which takes integral values from zero

upwards, is called the Rotational Quantum Number.
 Spectrum Of Rigid Rotator

In the rotational region, spectra are usually discussed in terms of

wave numbers.

 2 J J  1cm 1
EJ h
 
J (J=0, 1, 2, …)
hc 8 Ic
Where c is velocity of light, Is here expressed in cm s-1 .

  BJ J  1cm 1
J (A)

Where B, the rotational constant, is given by

h
B cm 1
8 2 Ic
From eq.(A) allowed energy levels

For J = 0, ε is zero => molecule is not

rotating

For J=1, the rotational energy is ε1= 2B

and a rotating molecule has its lowest

angular momentum

For increasing J values, εJ may have no

limit to the rotational energy

If we imagine the molecule to be in the ground
state, in which no radiation occurs

To raise the molecule to J= 1 state energy

absorbed will be

εJ1 – εJ0 = 2B – 0 = 2B cm-1

 J 0J 1  2Bcm1

Further for J=1 to J=2

 J 1 J  2  6 Bcm 1  2 Bcm 1  4 Bcm 1

In general,  J  J 1  BJ  1J  2  BJ J  1

 
 B J 2  3J  2  J 2  J 
Or
 J J 1  2BJ  1cm1

Thus a step wise raising of the rotational energy results in an

absorption spectrum consisting of lines at 2B, 4B, 6B, … cm-1.

we need only consider transition in which J changes by one unit –

all other transitions being spectroscopically forbidden, such a

result, it is called a selection rule,

Selection rule: ΔJ= ±1

1. Calculate the reduced mass and the moment of inertia of
NaCl using the mean internuclear distance of 2.36 A. The
atomic masses are Cl=35x10-3 kg mol-1 and Na=23x10-3kgmol-1.
Solution
The reduced mass is given as

1 1 1 m +m
= = 1 2
μ m1 + m2 m1m2

(35x10-3 kg mol-1)(23x10-3 kg mol-1)

or μ =
(35x10-3 kg mol-1+23x10-3 kg mol-1)(6.023x1023 mol-1)

= 2.304x 10-26 kg
The moment of inertia is given as
I = μr2 = (2.304x 10-26 kg) (2.36x10-10m)2

= 12.83 x 10-46kg m2
 Spectrum of Non-rigid Rotator

 We can see that rotational spectra of molecules show

an increase in bond length with J
 Our assumption of rigid bond is only an approximation.
 In fact, all bonds are elastic to some extent and the
increase in length with J reflects the fact that the more
quickly a diatomic molecule rotates the greater is the
centrifugal force tending to move the atoms apart.
 Spectrum of Non-rigid Rotator

Consequences of elasticity:
1. When the bond is elastic, a molecule may have vibrational energy
The bond will stretch and compress periodically with a certain
fundamental frequency dependent upon the masses of the atoms
and elasticity (or force constant) of the bond.
If the motion is simple harmonic, the force constant is given by :
k = 4π2 ω2c2μ
Where ω is the vibration frequency in cm-1. The variation of B and
J is determined by the force constant. The weaker the bond, the
more readily will it distort under centrifugal forces.
 Spectrum of Non-rigid Rotator

2. The second consequence of elasticity is that the

quantities r and B vary during a vibration.
When these quantities are measured by microwave
techniques many hundreds of vibrations occur during
a rotation and hence the measured value is an
average.
 Spectrum Of Non-rigid Rotator

The Schrodinger eq. may set up for non

rigid rotator
h2 h4
E J  2 J J  1    
2 2
J J 1 J
8 I 32 I r k
2 2 2

Or,
 j  E J hc  BJ J  1  DJ 2 J  12 cm 1

Where D is centrifugal distortion

constant, given by,
h3 1
D cm
32 4 I 2 r 2 kc

k is the force constant = 4π2 ω2c2μ

Selection rule:
The selection rule ΔJ = ±1 is valid whether molecule is rigid or
non rigid. The analytical expression for the transitions is as
follows:
ЄJ J+1 = B [(J+1)(J+2)-J(J+1)] – D[(J +1)2 (J+2)2 –J2(J+1)2]cm-1
= 2B (J+1)- 4D(J+1)3cm-1
It follows that the spectrum of a non-rigid rotator is almost
similar to that of a rigid molecule except that each spectral line
will undergo displacement towards the low frequency value and
the displacement increase with (J+1)3.
 INSTRUMENTATION
Source and Monochromator:
Reflex klystron valve is the main source of radiation in
microwave region.
Beam Direction:
The radiation emitted by klystron cannot be handled with
mirrors and lenses, but can be most advantageously
transmitted through hollow metallic conductors of such
geometry that the electric and magnetic fields can be utilized
to the greatest extent. These are known as wave guides.
Sample and Sample Space:
The sample is placed in a piece of evacuated wave-guide which
is closed at both ends by thin mica windows. Round holes are
made in the tube for evacuation purposes and for introduction
of the gas under test. The pressure of the gas is adjusted to
make the absorption line sharp.
Detector:
Quartz crystal is used as a detector. It is mounted on a
cartridge made up of a tungsten whisker held in point contact
with the crystal.

Spectrum Analyser:
It consists of an amplifier and an indicator which may be either
a cathode ray oscillograph or a pen and ink-recorder. The
vibration emitted by the quartz crystal produce an electric
signal which is amplified and then displayed as a pattern on an
oscilloscope screen or a recording on a chart by the pen and
ink recorder.
 INSTRUMENTATION

klystron Sample inlet

Crystal detector

Wave guide

oscilloscope

Klystron power supply amplifier

Microwave Spectrometer
 Classification of Molecules
1. Linear molecules:
 Atoms are arranged in a straight line.
e.g. HCl or OCS
The three directions of rotation may be taken as:
(a) about the bond axis
(b) end-over-end rotation in the plane of the paper
(c) end-over-end rotation at right angles to the plane. Here IA ≈ 0
and IB = IC C

A
Q P

B
 Since the moment of inertia is quadratic in the bond
lengths, the microwave spectrum yields the bond
lengths directly, provided the atomic masses are known.
 Examples of linear molecules are the diatomics such as
oxygen (O=O), carbon monoxide (C≡O), and nitrogen
(N≡N).
 Many tri-atoms are linear: carbon dioxide (O=C=O),
hydrogen cyanide (H-C≡N), and carbonyl sulphide
(O=C=S).
 Examples of larger linear molecules are chloroethyne
(HC≡CCl), and acetylene (HC≡CH).
2. Symmetric top:
 Symmetric tops have a three-fold or higher rotational
symmetry axis.
 Example - methyl fluoride, three hydrogen atoms are
bonded tetrahedrally to the carbon.
 The moment of inertia about the C-F bond axis is not
negligible.
 Symmetric tops: IB=IC≠IA IA≠0

H
H C F
H
Two subdivisions of this class
1. Prolate - Methyl fluoride, IB=IC>IA, then the molecule is
called prolate symmetric top
2. Oblate - If IB=IC<IA, it is referred to as oblate
An xample of this type (layer type) is boron trichloride,
which, as shown, is planar and symmetrical.
IA = 2IB = 2IC
3. Spherical top:
When a molecule has all three moments of inertia
identical, it is called spherical tops. They have cubical
symmetry.
e.g, CH4; IA=IB=IC.
4. Asymmetric top:
These molecules, to which the majority of substance
belong, have all three moments of inertia different:
IA≠IB≠IC
Simple example are H2O and CH2=CHCl
 Applications
Microwave spectroscopy is commonly used in physical chemistry to
determine the structure of small molecules (such as ozone, methanol,
or water) with high precision. However, microwave spectroscopy is not
useful for determining the structures of large molecules such as
proteins.
Microwave spectroscopy can be used for determining the symmetry
of the molecule. Eg. Xenon oxyfluoride molecule is having c4ν
symmetry. Since microwave spectrum of this molecule is a
characteristic of a symmetric top.
Calculation of inter atomic distances – isotopic
substitution.
Structural Organic chemistry – Example: Structural
determination of geometry of Benzonitrile
Inversion of spectrum of ammonia – In the spectrum of
ammonia each of the lines is split in to a doublet due to
inversion of the molecule – splitting takes place due to the
quantum mechanical tunnel effect due to the finite barrier
height and low mass of hydrogen atoms.
Microwave spectroscopy is successful in determining the
isotope abundance because each molecule possesses a
unique moment of inertia depending on the particular nuclei
present. From the relative intensity of the line or from the
integrated area, the abundance can be obtained.
Microwave spectroscopy is one of the principal means by
which the constituents of the universe are determined from
the earth. It is particularly useful for detecting molecules in
the inter stellar medium (ISM).

*********
5. Pure rotational (microwave) spectrum of the gaseous molecule CN consist
of a series of equally spaced lines separated by 3.7978 cm-1. Calculate the
internuclear distance of the molecule. The molar masses are 12C = 12.011
and 14N = 14.007 gmol-1.

Solution - The spacing between the lines = 2B = 3.7978 cm-1

therefore, B = 3.7978/2 = 1.8989cm-1

B = h
2
cm-1
8π Ic
6.626 x 10-34J s
I = h2 =
8π2Bc (8π2)(1.8989cm-1) (3 x 1010 cm s-1)

= 1.4742 x 10-46 kg m2

The reduced mass is given as follows

(m1/NA)(m2/NA) m1 m2
μ = =
(m1/NA)+(m2/NA) (m1+m2)NA
Where NA refers to the Avogadro’s number and m1, m2 are the atomic
masses of C and N respectively.
Thus,
(12.011g mol-1)(14.007g mol-1)
μ =
(26.018gmol-1)(6.022 x 1023 mol-1)

= 1.0737 x 10-23 g = 1.0737 x 10-26 kg

Since I = μr2
½
½ 1.4742 x 10-46kg m2
r = I =
μ 1.0703 x 10-26 kg

= 1.1717 x 10-10 m = 117 ppm

6. The pure rotational (microwave) spectrum of gaseous HCl consists of a series of
equally spaced lines separated by 20.80 cm-1. calculate the internuclear distance of
the molecule. The atomic masses are 1H = 1.673 x10-27 kg : 35Cl = 58.06 x 10-27 kg.

Solution
The spacing between the lines = 2B = 20.80 cm-1
B = 20.80/2 = 10.40 cm-1

B = h
2
cm-1
8π Ic
6.626 x 10-34J s
I = h2 =
8π2Bc (8π2)(10.40 cm-1) (3 x 1010 cm s-1)

= 0.2689 x 10-46 kg m2 Joule= kg m2 s-2

The reduced mass is given as follows
m1 m2
μ =
(m1+m2)NA

Where m1 and m2 are the atomic masses of H and Cl, respectively.

Thus,

(1.673 x 10-27 kg)(58.06 x 10-27 kg)

μ =
(1.673 + 58.06) x 10-27 kg

(1.673 x 58.06)10-27
= kg = 1.626 x 10-27 kg
59.74

Since I = μr2
½
½ 0.2689 x 10-46kg m2
r = I =
μ 1.626 x 10-27 kg

= 1.29 x 10-10 m = 129 pm

 Problems
• What are the degeneracies of the following diatomic rotational energy
levels: (a) 0, (b) h2/4π2I, (c) 6 h2/4π2I; where I is the moment of inertia.
Solution
It is known that for a diatomic molecule the rotational energy levels are
given by

EJ = h2 J(J+1) Where J= 0,1,2,3,…..

8π2I

Here J is the rotational quantum number.

The degeneracy, gJ of rotational level is given by
gJ = 2J+1
(i) EJ=0 J=0

hence gJ=1

(ii) EJ = h2 J(J+1)
8π2I
2
since, EJ = h
4π2I
therefore, J(J+1)=2
when J=1
therefore, gJ=2 × 1 + 1 = 3

(iii) EJ = h2 J(J+1)
8π2I

therefore, J(J+1) = 12
or J=3
or gJ= (2 × 3)+1 = 7
 Rotation of a 3D object is complex and for
convenience, it is resolved in to 3 mutually
perpendicular components through the center of
gravity.
 Thus a body can have three principal moment of
inertia, designated as IA, IB and IC
 Molecules may be classified in to groups based on the
relative values their three principal moment of inertia
(based on their shape).