Microwave spectroscopy

Microwave spectroscopy is also known as rotational

spectroscopy lies in the wavelength region: 1 cm-100μm
Generally, the microwave spectra obtained in most of
the molecules are absorption spectra

Recent years microwave spectroscopy is a great asset in

the study of various problems in physics, chemistry,
electronics and even astronomy.

Particularly, it is very useful in the determination of the

structures of those molecules which do not give good
results by using Raman and infrared spectroscopy
accuracy of the order of 0.001 to 0.005 A ◦.
 A molecule such as HCl in which one atom
carries a permanent net positive charge and the
other a net negative charge is said to have a
permanent electric dipole moment. Thus fluctuating
electric component of EMR interact with the
molecule, energy can be absorbed or emitted and
the rotation gives rise to a spectrum

 Molecules such as H2 or Cl2, on the other

hand , in which there is no such charge separation,
have a zero dipole moment. Thus no interaction can
take place and the molecule is microwave inactive
 Classification of molecules

1. Linear molecules: Molecules in which all the atoms are

arranged in a straight line. Example: HCl, OCS etc. 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 moment of Inertia about the bond axis is very

small . So approximately IA is taken equal to zero.
Linear molecule

IA = 0
IB=IC
2. Symmetric tops:
Example: methyl fluoride (tetrahedral structure)
H
H C F IB=IC≠IA
H IA ≠ 0
As in the case of linear molecules, the end-over-
end in plane and out of plane rotations are
identical and we have IB=IC
If IB=IC > IA Prolate eg: methyl fluoride
IB=IC < IA Oblate eg: Boron trichloride
BCl3 is planar and symmetrical →IA =2IB=2IC
3. Asymmetric tops: Majority of molecules or
substances belong to this class, in which all
three moments of inertia different :
IA≠IB≠IC≠0
Eg: Water and vinyl chloride
O H H
H H C C
H Cl
4. Spherical tops :
Example: Methane (CH4), Tetrahedral

IA=IB=IC

In fact these molecules do not possess dipole

moment. They are microwave inactive
The moment of inertia for a diatomic (linear) rigid rotor

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 x r2 = r2
m1 + m2
ro = r 1 + r 2 ------------------------------------(1)

m1r1 = m2r 2 --------------------- (2)

I = m1r12 + m2r22 ------------------- (3)

= m2r2r1 + m1r1r2 ----------------(4)

r r m1 +m2)
I = 1 2 ( ----------------(5)

But from eq. 1 and 2

r2 = r o - 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)

Rotational energy levels:
Rotational energy levels may in principle be calculated by
solving the Schrodinger’s eqn.
i.e. EJ = (h2/ 8π2I) [J(J+1)] Joules
Where J= 0,1,2,3………
In rotational region spectra are generally expressed in
terms of wave number,
ЄJ = EJ/hc = (h/8 π2Ic) [J(J+1)] cm-1
ЄJ = [J(J+1)] B cm-1

Where B is known as rotational constant

Selection rules for the rotational spectrum:
The allowed energy levels is shown in the following diagram.
Only those transitions are allowed where, ΔJ = + 1
Here rotational quantum number J = 0,1,2 etc.,

If ЄJ = 0 J=1

= 2B cm -1

ЄJ = 1 J=2

= 6B cm -1 - 2B cm -1 = 4B cm-1

In general to raise the molecule from state J to state J+1 will be given as:
ЄJ J+1 = [B(J+1)(J+2) – BJ(J +1) ]cm-1
= B [J2 + 3J +2- (J2+J)
=2B (J+1) cm-1
 Non rigid diatomic molecules-rotational spectra,
• We can see that rotational spectra of molecules show
that there is a increase in bond length with J so our
assumption of rigid bond is only an approximation.

• In fact , of course all bonds are elastic to some extent

and the increase in length with J merely reflects the fact that
the more quickly a diatomic molecule rotates the greater is
the centrifugal force tending to move the atoms apart.
The Rotational energy levels for a non-rigid molecule may be calculated by solving
the Schrodinger’s eqn. as follows:
h2 h4
EJ = J(J+1) - J2(J+1)2 Joules
8π2I 34 π4I2r2k

or ЄJ = EJ/hc = BJ(J+1)- D J2(J+1)2 cm-1

For a simple harmonic force field

Where D is centrifugal distortion constant .

D is given by h3 / 34 π4I2r2kc cm-1

Which is a positive quantity.

If the field is anharmonic , the expression becomes:
ЄJ = EJ/hc = BJ(J+1)- D J2(J+1)2 + H J3(J+1)3 + K J4 (J+1)4 …cm-1
Where H,K etc., are small constants dependent upon the geometry of the molecule

D= 16B3π2c2μ / k = 4B3/ ω2
Consequences of elasticity:
1.When the bond is elastic, a molecule may have vibrational energy

i.e., 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
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.
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.
Two useful measurements can be made from the D
value.

(a) The value of vibrational frequency ω can be found,

(b) Determine the J value of the line in an observed
spectrum.
 J Rigid rotator Non-rigid rotator
10

2
1
0
0 2B 4B 6B 8B 10B 12B 14B 16B 18B 20B

Rigid

Non- rigid

0 2B’ 4B’ 6B’ 8B’ 10B’ 12B’ 14B’ 20B’

 Intensities of spectral lines
The relative intensities of spectral lines have been
found to depend upon the relative populations of the
energy levels. Even at room temperature many of the
diatomic molecules are present in the excited state
energy levels.
The energy level population is given by the Boltzmann
distribution of molecules.
So the intensity of the rotational energy levels is given
by
Intensity α NJ/N0 = e-EJ/kT
However rotational energy levels are degenerate, their degeneracy( gJ)
for a diatomic molecule being given by ;
gJ = 2J+ 1
In other words, for a given value of J, the energy level is (2J+1)-
degenerate. For J=0, gJ =1.
For J= 1, gJ = 3;
For J= 2, gJ= 5 and so on.
Thus, the intensity of the spectral line can be determined by the
product of the degeneracy and Boltzmann exponential factor.
Thus,
Intensity α NJ/N0 = (2J+1) e-EJ/kT

Since EJ = hc ЄJ
ЄJ = B J(J+1)
We have NJ/N0 = (2J+1) e-BJ(J+ 1)hc/kT
The quantity NJ/N0 is plotted versus J for a rigid
diatomic molecule at room temperature as
shown in the picture.
 It can be seen that the relative intensity passes
through a maximum.
The value of J corresponding to the maximum in
population is given by ;
J max = [(kT/2hcB) ½ – 1/2]
The Jmax be rounded off to a nearest integral
value.
Problem: Calculate Jmax for a diatomic molecule
for which at 300K, the rotational constant is
1.566 cm -1
Solution: J max = [(kT/2hcB) ½ – 1/2]
[(1.38 x 10 -23 J/K) x 300 K] 1/2

= - 1/2 = 7.56 = 8
[ 2 x (6.626 x 10-34 J s )(3 X 1010 cm s-1)(1.566 cm s-1)
 Effect of Isotopic Substitution
When a particular atom in a molecule is
replaced by its isotope- an element identical in
every way except for its atomic mass-the
resulting substance is identical chemically with
the original. In particular there is no appreciable
change in internuclear distance on isotopic
substitution, however, there is a change in the
total mass and hence in the moment of inertia
and B values for the molecule.
Consider CO as an example, we see that on going from 12C16O to
C O there is a mass increase and hence a decrease in the B
13 16

value. If we designate the 13C molecule with a prime we have

B˃B1. This change will be reflected in the rotational energy levels
of the molecule. The relative lowering of the 13C levels with
respect to those of 12C. The spectrum of the heavier species will
show a smaller separation between the lines (2B1)than that of
the lighter one(2B).
Gilliam et al., found the first rotational absorption of 12C16O to be
at 3.84235 cm-1, while that of 13C16O was at 3.67337 cm-1. The
value of B determined from these figures are B = 1.92118 cm-1
and B1 = 1.83669 cm-1. Where the prime refers to the heavier
molecule.
We have,

B/B1 = [(h/8 π2Ic) x (8 π2I1c /h ] = I1/I =μ1/μ = 1.046

μ1/μ = 1.046 = [15.9994 m1/ 15.9994 + m1] x [(12 +

115.9994) / 12 x 15.9994]
From which m1 , the atomic weight of carbon-13, is found to
be 13.0007. This is within 0.02 per cent of the best value
obtained in other ways. So microwave studies can give
directly an estimate of the abundance of isotopes by
comparison of absorption intensities.
 Stark Effect
• The Stark effect is the shifting and splitting of spectral lines of
atoms and molecules due to presence of an external electric field.

J
E
In the above figure M is the projection of J along the
external electric field. The energy EJM in the presence of
the field is given by
EJM = EJ + a J,M Є + ½ b2 J,M Є2

Where EJ is the energy of the rotation in the absence of

the field and aJ,M and bJ,M are the first and second order
Stark effects. If the dipole μ has a component along the
direction of J, we get the first order Stark effect; if μ is
perpendicular to J, we get the second order Stark effect.
 INSTRUMENTATION

klystron Sample inlet

Crystal detector

Wave guide

oscilloscope

Klystron power supply amplifier

Microwave Spectrometer
Source and Monochromator:
Reflex klystron valve is the main source of radiation in microwave
region. (A klystron is a specialized linear-beam vacuum tube (evacuated
electron tube).

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 of detected energy 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.
 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.

 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

 Different conformational isomers can be studied provided they have

different moments of inertia.
 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.

 Useful for detecting molecules in the interstellar medium (ISM).

One of the early surprises in interstellar chemistry was the
existence in the ISM of long chain carbon molecules, like
fullerenes which led to the award of the 1996 Nobel prize in
chemistry to Kroto, Smalley and Curl.

 Microwaves are used by astronomers to learn about the structure

of nearby galaxies, including our own Milky Way!
 Limitations of Microwave Spectroscopy

• Microwave spectroscopy is not useful for determining

the structures of large molecules such as proteins.

• Applicable only to gaseous samples as rotational

energy levels are not quantized in case of liquids and
solids.

• Cannot detect the presence of particular molecular

groupings in a sample, like –OH, -CH3, -COOH, NH2
etc
1. Calculate the reduced mass and the moment of inertia of NaCl using the
o
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 m 1 + m 2 m 1m 2

(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
2. The rotational spectrum of HCl shows a series of lines separated by
20.6cm-1. Find the moment of inertia and the internuclear distance.
Given atomic masses of H= 1.008 g and Cl = 35.5 g respectively.
Solution
Since 2B = 20.6 cm-1
B = 10.3 cm-1 = 10.3x 102 m-1

Also B = h
8π2Ic
h (6.626x10-34 kg m2 s-1)
I = =
8π Bc
2
8 x (22/7)2 x (10.3x102m-1)(3x108m s-1)

= 2.715 x 10-47 kg m2

Now I = μr2

r = I
μ
 m 1m 2 (1.008x10-3 kg)(35.5x10-3 kg)
μ = m1+m2 =
(1.008 x 10-3 kg + 35.5 x 10-3 kg)(6.023x1023 mol-1)

Therefore, = 1.628 x 10-27kg

r = I
μ

2.655 x 10-47 kg m2
=
1.628 x 10-27kg

= 1.276 x 10-10 m
3. The internuclear distance (i.e, bond length) of carbon
monoxide molecule is 1.13 A . Calculate the energy (in joules
o

and in eV) of this molecule in the first excited rotational level.

The atomic masses are 12C=1.99x10-26 kg; 16O = 2.66x10-26 kg.

Solution. r = 1.13 A = 1.13 x10-8cm = 1.13 x 10-10m

o

m 1m 2 (1.99x10-26 kg)(2.66x10-26 kg)

μ = m1+m2 = = 1.14 x 10-26 kg
(1.99+2.66) x 10-26 kg

Hence the moment of inertia is as follows:

I = μr2 = (1.14 x 10-26 kg) (1.13x10-10m)2 = 1.46 x 10-46 kg m2

The rotational energy levels of a rigid diatomic molecule are given by

EJ = h2 J(J+1) joule
8π2I
For the first excited rotational level, J=1. therefore,

h2 x 1(1+1) h2
EJ = = joule
8π I
2
4π I2

(6.626 x 10-34Js)2
= 7.61 x 10-23 joule
4π2 (1.46 x 10-46 kg m2)

Since 1 eV = 1.602 x 10-19 J

7.61 x 10-23J
EJ = = 4.76 x 10-4 eV
(1.602 x 10-19 J(eV)-1
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
cm-1
8π2Ic
6.626 x 10-34J s
I = h =
8π Bc
2
(8π2)(1.8989cm-1) (3 x 1010 cm s-1)

= 1.4742 x 10-46 kg m2 Joule= kg m2 s-2

The reduced mass is given as follows

(m1/NA)(m2/NA) m 1m 2
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 kg m
-46 2

r = I =
μ 1.0703 x 10-26 kg

= 1.1717 x 10-10 m = 117 pm

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
cm -1
8π2Ic
6.626 x 10-34J s
I = h =
8π Bc
2
(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
m 1m 2
μ =
(m1+m2)NA

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

. 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
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