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Subject Chemistry

Paper No and Title 8 : Physical Spectroscopy

Module No and Title 13: Microwave Spectroscopy

Module Tag CHE_P8_M13

CHEMISTRY PAPER No. : 8 (PHYSICAL SPECTROSCOPY)

MODULE No. : 13 (MICROWAVE SPECTROSCOPY)
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TABLE OF CONTENTS
1. Learning Outcomes
2. Introduction

3. Rotational Spectra

4. Appearance of Rotational Spectra

5. Summary

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1. Learning Outcomes
In this module, we shall

• learn about microwave spectroscopy. In this branch of spectroscopy, rotational transitions

are observed.
• be able to interpret rotational spectra, get information about molecular dimensions and
atomic masses.

2. Introduction
Like electronic energy levels, the rotational energy levels are quantized. This means that, when
transitions occur between these energy levels, absorption and emission of radiation can take
place, leading to discrete lines in the spectra. Since the energy levels are relatively close to each
other, the absorptions and emissions fall in the low energy microwave region. For this reason,
rotational spectroscopy is also known as microwave spectroscopy.

3. Rotational Spectra
Solution of the rotational Schrödinger equation gives the allowed energy levels as

E J = BJ ( J + 1) (1)

where B is a quantity known as the rotational constant and J is the rotational quantum number,
which can take on positive integer values, including zero. The rotational constant B has the
dimension of energy (Joule) and is expressed as

!2
B= (2)
2I

where I is the moment of inertia of the molecule, which is equal to µR2, µ being the reduced
mass of the molecule and R the internuclear distance.

Like other transitions, rotational transitions are also governed by selection rules. For a transition
from a state with rotational quantum number J” to another state J’, the transition dipole moment
integral is given by

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M J ' J " = ψ J* ' µˆψ J " dτ = µ 0 ψ J* 'ψ J " dτ

∫ ∫ (3)

where µ0 is the permanent dipole moment of the molecule. Since the intensity of a transition is
proportional to the square of the transition dipole moment, it is obvious that molecules that do not
possess a dipole moment do not exhibit rotational spectra. In other words, they cannot interact
with microwave radiation and are said to be microwave inactive. Examples are all homonuclear
diatomic molecules like H2, N2, O2, and F2. All tetrahedral and octahedral molecules like CH4 and
SF6 are also microwave inactive, as are other symmetrical molecules like benzene. However,
molecules like H2O, which possesses a dipole moment are microwave active. The domestic
microwave oven operates at the microwave rotational frequency of water. The water in the food
gets rotationally excited and heats up, cooking the food.

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Example 1. Which of the molecules H2, NO, N2O can have a pure rotational spectrum?

Solution

All except H2.

Example 2. Which of these molecules will show a pure rotational (microwave) spectrum: CH4,
CH3Cl, CH2Cl2, CH2=CH2, benzene, SF6?

Solution

CH3Cl and CH2Cl2.

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For rotational spectra the gross selection rule is:

All molecules that do not possess a permanent dipole moment are microwave inactive.

Even for molecules that possess a permanent dipole moment, all transitions are not allowed.
Detailed calculations show that the only transitions that are allowed are those for which

ΔJ = ±1

This selection rule can be rationalized on the basis of the conservation of angular momentum. The
photon has an intrinsic angular momentum of one unit. Absorption or emission of one photon can
therefore increase or decrease the rotational quantum number by one unit.

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Let us first consider absorption spectra. The energy of the photon that is absorbed is the
difference in energies between these two states, i.e.

hν J → J +1 = Erot ( J + 1) − Erot ( J ) = B( J + 1)( J + 2) − BJ ( J + 1) = 2B( J + 1) (4)

Figure 1. Rotational energy levels and transitions between them

The lowest value of the rotational quantum number is zero and absorption of a photon can take
the molecule to the J = 1 level, resulting in absorption of a photon of energy 2B. The J = 1 → 2
transition occurs at 4B. Subsequent lines are observed at 6B, 8B, 10B, etc. Rotational spectra
should therefore consist of equally spaced lines with spacing of 2B between them, from which the
rotational constant can be obtained.

Before we discuss the utility of this information, let us first look at the appearance of the spectra,

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4. Appearance of Rotational Spectra

After the selection rules, the next important consideration is the relative populations of the
various levels. We have already seen that rotational energy spacings are small, and so a number
of rotational energy levels are occupied at room temperature, since ΔErot << kBT, where kB is the
Boltzmann constant and T is the temperature in Kelvin. At room temperature, the value of kBT is
~4×10-21 J, while rotational energy spacings are much smaller (~10-23 s). According to the
Boltzmann distribution, the ratio of populations of the excited and ground state is given by

NJ
= g J e − ΔE J / k BT (5)
N0

where gJ is the degeneracy of the J-th level (degeneracy of the J = 0 level is 1) and ΔEJ is the
energy difference between the J-th level and the J =0 level, which is equal to EJ, since the J = 0
level has zero energy.

There are two opposite factors operating. One is the rapid linear increase in the degeneracy, 2J +
1, with increasing J and the other is the exponential decrease with increasing J. The net result is
that the population initially increases because of the initial dominance of the degeneracy term,
goes through a maximum and then decreases (Fig. 2).

Figure 2. Variation of the population of rotational states with quantum number

We can analytically derive an expression for Jmax, the value of J for the most populated state, by
differentiating expression (5) with respect to J and setting it equal to zero. Rewriting equation (5)

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⎛ − E J ⎞
N J = N 0 (2 J + 1) exp⎜⎜ ⎟⎟
⎝ k B T ⎠

dN J ⎡ B ⎤
= e − E J / k BT ⎢2 − (2 J + 1) (2 J + 1)⎥ = 0
dJ ⎣ k BT ⎦
B
⇒ (2 J + 1) 2 =2 (6)
k BT
1 2k B T 1 k BT 1
J max = − = −
2 B 2 2B 2

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Example 1. Calculate the ratio of the number NJ to N0 of molecules in a sample of HI at (a) 300
K and (b) 1000 K having rotational quantum numbers J = 5 and J = 0 (I = 4.31×10-47 kg m2) (c)
Calculate the value of J at the maximum NJ at these two temperatures.
Solution
(a) T = 300 K
NJ
= (2 J + 1) exp(− E J / k B T )
N0
⎛ 30h 2 ⎞
= 11exp⎜⎜ − 2 ⎟
⎟
⎝ 8π Ik B 300 ⎠
= 0.584
(b) At 1000 K,

NJ
= (2 J + 1) exp(− E J / k B T )
N0
⎛ 30h 2 ⎞
= 11exp⎜⎜ − 2 ⎟
⎟
⎝ 8π Ik B 1000 ⎠
= 0.756

!2
(c) B = = 1.29 × 10 −22 J
2I

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k BT 1
J max = −
2B 2
1.38 × 10 − 23 T 1
= − 22
−
2 × 1.29 × 10 2
= 5.35 × 10 − 2 T − 0.5

At 300 K, Jmax = 4.00-9.5 = 3.5 ≈ 4

At 1000 K, Jmax = 6.8 ≈ 7

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We note that Jmax moves to a higher value when the temperature is raised. The intensities of the
spectral lines therefore depend on the temperature.

Example 2. The moment of inertia of the H35Cl molecule is 2.644×10-47 kg m2. Prepare relative
population curves, NJ/N0 versus J for HCl at 300 K and 1000 K.

Solution

NJ ⎛ J ( J + 1)! 2 ⎞
= (2 J + 1) exp⎜⎜ − ⎟ = (2 J + 1) exp(-15.23J(J + 1 ) / T )
N0 2 Ik B T ⎟
⎝ ⎠

The relative population versus J graph is shown below

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The rotational energy of the level which has the highest population is, therefore,

E rot (max) = J max ( J max + 1) B

⎛ k T 1 ⎞⎛ k T 1 ⎞
= ⎜ B − ⎟⎜ B + ⎟ B
⎜ 2 B 2 ⎟⎠⎜⎝ 2 B 2 ⎟⎠
⎝
(7)
⎛ k T 1 ⎞
= ⎜ B − ⎟ B
⎝ 2 B 4 ⎠
k BT B
= −
2 4
~
k BT B
Except at very low temperatures, >> ; the energy of the most populated level is, therefore,
2 4
k BT
≈ .
2

Besides population, the other factor that governs the intensity maximum is the magnitude of B.
Since it appears in the exponential term, larger the value of B, faster is the exponential decay.

Example 3. What is the value of J in the most highly populated rotational level of ICl at room
~
temperature? ( B = 0.114 cm-1)?
Solution
~
Since B = B/hc, the expression for the most populated level becomes

k BT 1
J max =~ −
2 B hc 2
Substitution of the various values gives
Jmax = 29.65.
The nearest whole number is 30.
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We notice that the Jmax value is extremely large because the rotational constant is extremely small
in this case.

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.5. Summary
• Pure rotational transitions are observed in the microwave region.
• There are two selection rules governing rotational transitions:
o The gross selection rule is that the molecule must possess a permanent dipole
moment.
o The second selection rule is that the rotational quantum number must change
by one unit.
• The absorption spectrum gives rise to a spectrum containing lines with spacing equal to
twice the rotational constant.
• Because of the small spacing, many of the rotational states are occupied at room
temperature.
• The degeneracy of an energy level increases linearly with J, but the population decreases
with increasing J. As a result, the population goes through a maximum at some J.
• The rotational level having the largest population shifts to higher J when the temperature is
increased.
• It also depends on the value of the rotational constant. Smaller the rotational constant,
larger is the Jmax.

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