Microwave Spectroscopy

Introduction

Free atoms do not rotate or vibrate. For an oscillatory or a rotational motion of a

pendulum, one end has to be tied or fixed to some point. In molecules such a fixed point
is the center of mass. The atoms in a molecule are held together by chemical bonds. The
rotational and vibrational energies are usually much smaller than the energies required
to break chemical bonds. The rotational energies correspond to the microwave region of
electromagnetic radiation (3x1010 to 3x1012 Hz; energy range around 10 to100 J/mol)
and the vibrational energies are in the infrared region (3x10 12 to 3x1014 Hz; energy
range around 10kJ/mol) of the electromagnetic radiation. For rigid rotors (no vibration
during rotation) and harmonic oscillators (wherein there are equal displacements of
atoms on either side of the center of mass) there are simple formulae characterizing the
molecular energy levels. In real life, molecules rotate and vibrate simultaneously and
high speed rotations affect vibrations and vice versa
Rotational energy levels of diatomic molecules

A molecule rotating about an axis with an angular velocity ω

C=O (carbon monoxide) is an example. The rotational kinetic energy
expression is given in classical mechanics as
Rotational kinetic energy, E rot = ½ Iω2
where I is moment of inertia, I = μr2
where μ = m1m2/m1+m2, is the reduced mass, m1 and m2 are the masses
of the two atoms and r is the bond length

In terms of angular momentum J , the rotational kinetic energy E rot is

J = Iω → Erot = J2/2I
This is another form of classical expression.
In quantum mechanics
Replace angular momentum J by the operator form and obtain the
corresponding operator form for the Hamiltonian (which is only
rotational kinetic energy). The form turns out to be
 Where is Laplacian operator and ħ = h/2π

You know the solution for operator from hydrogen atom.

Assume a rigid diatomic molecule (bond lengths do not change.) The coordinate r is a
constant, not required. We need to consider only θφ the equation. It is possible to
derive formally the square of the total angular momentum operator using spherical
polar coordinates and show that it has the same form as the differential operator for the
θφ equation of the hydrogen atom. It will not be done here but will be assumed.

Hence the angular solutions of the hydrogen atom are the eigen functions of this
Hamiltonian.

Where J = 1,2,3.. and

K = −J, −J+1….J−1, J for each J
For each J, there are (2J+1) K values namely K = -J, -J+1, ..., J-1, J. Hence the
eigenfunctions are (2J+1)-fold degenerate for each J.
For example, for J = 1, K can have three values, K = -1, K = 0 and K = 1. For J
= 2, K can have five values, K = -2, -1, 0, 1 and 2 and so on.

Rotational energy is thus quantized and is given in terms of the rotational quantum
number J.

where
Rotational energy levels of a rigid diatomic molecule and the allowed transitions.
Rigid rotor energy levels are not equally spaced.
Rigid rotor spectrum consists of equally spaced lines.
The only molecules that can have microwave transitions are those which have a
permanent dipole moment.
Both of these results are from quantum mechanics and are experimentally
verified.

The selection rule for a rotational transition is,

In addition to this requirement, the molecule has to possess a dipole moment. As a

dipolar molecule rotates, the rotating dipole constitutes the transition dipole
operator μ. Molecules such as HCl and CO will show rotational spectra while H 2,
Cl2 and CO2 will not. The rotational spectrum will appear as follows
 E(J) = B J(J+1) J+3 3
E(J+1) = B(J+1)(J+2) 2B

E(J+1)− E(J) = B(J+1)(J+2) − B J(J+1) J+2 2

E(J+1)− E(J) = 2B(J+1) 2B
J+1 1
J = 0,1,2,3…..
2B
E(J+1)− E(J) = 2B,4B, 6B, 8B….. J 0
ΔJ =±1
 Rotational spectrum of a rigid diatomic.

Study one simple example below: Examine the dimensions first:

I =μr2 →ML2
B = h/8π2Ic→ ML2T−1/ML2LT−1 =L−1

Rotational angular momentum is ħJ

the magnitude of which is also quantized. There are (2J+1) eigen functions
(K=-J to +J ) for any J, all having the same energy. Therefore rotational
energy levels for a given J are (2J+1) fold degenerate
Example problem: for carbon monoxide you are given B = 1.92118 cm -1
Mass of carbon atom = 19.92168x10-27 Kg
Mass of oxygen atom = 26.56136x10-27 Kg
Calculate the bond distance r.

ICO = h/8π2cB = 14.5695 × 10−47 Kgm2

μ = (m1m2/m1+m2) Kg = 11.3836 × 10−27 Kg
I = μr2
r = √I/μ = 0.1131 nm = 1.131 Å

Similar manipulations can be made for other diatomic molecules. The

value of B is usually obtained from the pure microwave spectra of
molecules in the gas phase. Rotations are restricted in the liquid phase
and are arrested in the solid phase. Hence pure microwave spectra cannot
be obtained by other means. If the spectrum is regular, then the spacing
between two successive lines is 2B from which we can calculate the bond
distances.
 Intensities of microwave spectra and sample spectra

Intensity of a microwave transition line is proportional to the number of molecule

undergoing that transition.

The number of molecules in the level J is proportional to

(2J + 1)e−BJ(J + 1)hc/KBT
Where (2J +1) is the degeneracy factor and e −BJ(J + 1)hc/KBT = e−EJ/KBT is the Boltzman
factor. Where B is Boltzman constant and T is the temperature

If N0 is the total number of molecules, then the ratio is

PJ = NJ/N0 = (2J + 1)e−BJ(J + 1)hc/KBT / ∑ (2J + 1)e−BJ(J + 1)hc/KBT (all possible energy level J)

In particular the number ratio of upper level to lower level

NJ +1 /NJ = (2J + 3)e−Bhc(J + 1)(J +2)/KBT / (2J + 1)e−Bhc(J + 1)/KBT

NJ +1 /NJ = (2J + 3)e−2Bhc(J + 1)/KBT / (2J + 1)

Both the equal line spacing and the Boltzmann distribution of intensities are
observed in the experimental spectrum of HF shown below.
 Classification of molecular rotors

In quantum mechanics the free rotation of a molecule is quantized, so that

the rotational energy and the angular momentum can take only certain fixed values,
which are related simply to the moment of inertia, I, of the molecule. For any
molecule, there are three moments of inertia: I A, IB and IC about three mutually
orthogonal axes A, B, and C with the origin at the center of mass of the system. The
general convention, used in this article, is to define the axes such that I A ≤ IB ≤ IC with
axis A corresponding to the smallest moment of inertia. Some authors, however, define
the A axis as the molecular rotation axis of highest order

Spherical tops (spherical rotors)

All three moments of inertia are equal to each other. I A = IB = IC examples
phosphorus tetramer (P4), carbon tetrachloride (CCl4) and other
tetrahalides, methane (CH4), silane, (SiH4), sulfur hexafluoride (SF6) and other
hexahalides. The molecules all belong to the cubic point groups T d or Oh.
 Linear molecules.
For a linear molecule the moments of inertia are related by I A << IB = IC . For most
purposes, IA can be taken to be zero. Examples of linear molecules
include dioxygen, O2, dinitrogen, N2, carbon monoxide, CO, hydroxy radical,
OH, carbon dioxide, CO2, hydrogen cyanide, HCN, carbonyl sulfide, OCS, acetylene
(ethyne, HC≡CH) and dihaloethynes. These molecules belong to the point groups
C∞v or D∞h.

Symmetric tops (symmetric rotors)

A symmetric top is a molecule in which two moments of inertia are the same,
IB = IC or IA = IB . a symmetric top must have a 3-fold or higher order rotation axis
spectroscopists divide molecules into two classes of symmetric
tops, , Oblate symmetric tops (saucer or disc shaped) with IA = IB < IC .
and Prolate symmetric tops (rugby football, or cigar shaped) with I A < IB = IC
Examples
Oblate: benzene, C6H6, ammonia, NH3, xenon tetrafluoride, XeF4
Prolate: chloromethane, CH3Cl, propyne, CH3C≡CH
Asymmetric tops (asymmetric rotors) The three moments of inertia have different
values. IA ≠ IB ≠ IC Examples water, H2O and nitrogen dioxide, NO2 whose symmetry
axis of highest order is a 2-fold rotation axis. Most large molecules are asymmetric tops.

Problem 1.
Classify each of the following molecules as a spherical, symmetric or asymmetric top
molecule
(a) CH4 b) CH3Cl c) CH2Cl2 d) CHCl3 e) CCl4 f) SF6 g) H2O h) C2H6 i) Benzene j) NH3
k) O3
Solution
CH4 - Spherical top CH3Cl - symmetric top CH2Cl2 - asymmetric top CHCl3 -
symmetric top CCl4 - spherical top SF6 - spherical top H2O - asymmetric top C2H6 -
symmetric top Benzene - symmetric top NH3 - symmetric top O3 - asymmetric top
Problem 2.
The frequency of microwave transition from J=0 to J=1 for 12C16O is given as
3.845 cm-1. Calculate the C=O bond distance using a rigid rotor model.
(h = 6.627 × 10−34 Js, c = 2.99 × 108 ms-1, NA = 6.023 × 1023 )

Solution

1. ΔE for the transition from J = 0 to 1 is equal to 2B where B = h/8π2Ic is in wave

number units.
2. I = μr2 , where is the reduced mass and r is the internuclear (bond) distance.

3. 2B = 2h/8π2μr2c = 3.845 cm-1 = 384.5 m-1

use SI units for calculations

r = √h/8π2μcB

Where r will be in meter, h is in joule.sec, μ is in kg, c is in ms-1 , and B is in m-1 .

 μ = m1m2/m1+m2 = 16×12×0.001/(16+12)×6.023×1023 = 1.138×10-26 kg

h/8π2μcB = 6.626×10-34 J.s /8×π2×1.138×10-26 kg× 2.99×108 ms-1×192.25m-1

h/8π2μcB = 1.283×10-20 m2

r = √h/8π2μcB = 1.133×10-10 m = 1.133 Å

Problem 3.

Determine the ratio of population in J’=2 and J”=1 states for 12C16O at room temperature
given that the rotational constant for the molecule is 1.923 cm -1 KB = 1.381* 10 -23 JK-1,
h = 6.627* 10-34 Js, c = 2.99*108 ms-1