Brief Article on Diatomic Molecules (Rigid

Rotors)

December 17, 2014

Rotational Spectra

Incident electromagnetic waves can excite the rotational levels of molecules provided they have an electric dipole moment. The spectra usually lies in Microwave region.
How? The electromagnetic field of the electromagnetic waves exerts a
torque on the polar molecule.
The rotational energies for rigid molecules can be found with the aid of the
Schrodinger equation.

1.1

Energies of Rigid Rotors

The classical energy of a freely rotating molecule can be expressed as rotational

kinetic energy

1
E=
Ix x2 + Iy y2 + Iz z2
2
For a diatomic molecule the rotational energy is obtained from the Schrodinger
equation with the Hamiltonian expressed in terms of the angular momentum
operator.
L2
J(J + 1)h2
H =
=
= E
(1)
2I
2I
Therefore,
hc
J(J + 1)h2
E=h
=
=

2I
From the above equation we conclude :
I
1

I
The energy is generally expressed in wave number units
 = E/c = BJ(J + 1)cm 1
where B = h
2 /2Ic is called the rotational constant.
1

(2)

1.2

Energies of Non-Rigid Rotors (Centrifugal distortion)

For a non rigid rotor, the energy levels are given by

=

2
h
h4
J(J + 1) 2 2 J 2 (J + 1)2 = BJ(J + 1) DJ 2 (J + 1)2
2Ic
2I r kc
4

where D = 2I 2hr2 kc is the centrifugal distortion constant. k is the force constant

and and r is the radius of rotor. If we define
= /c,
D = 4B 3 /

Lets give an estimate of the orders of magnitudes :

103 cm1 ,
B 10cm1
so, D 103 cm1 .
Thus, D is usually negligible. The selection rule for non-rigid rotor is stll
given as, J = 1. The energy (in cm1 ) absorbed in a transition from state
J to J + 1 is given by
J+1 J = 2B(J + 1) 4D(J + 1)3
In consequence, the spacing between lines is not constant, as in the rigid rotor
approximation, but decreases with increasing rotational quantum number.
These results for Diatomic molecules hold for other Linear molecules in general.

Vibrational Spectra

Vibrational spectra is exhibited by molecules whose dipole moment changes

during vibration. The spectra usually lies in Infrared region. There may be
motions combining vibrational and rotation giving rise to a rich spectrum. We
assume that the molecular vibration follows simple harmonic motion, or that
the interatomic force between two atoms may be assumed to obey Hookes law
type of force.
Energy of harmonic Oscillator is quantized according to the formula
1
En = (n + )h0
2
where n takes value 0, 1, . . . , and 0 is the oscillation frequency. Wave number
is defined as
En
1
n =
= (n + )h
0
hc
2
where, 0 = /c.
The selection rule for transition between two vibrational states is n = 1.
For any transition, the vibrational spectra has a single wave number, 0 , because
the energy levels are equally spaced.
2

2.1

Real Molecules

However the real molecules do not obey Hookes Law. The wave number for
them is given by
1
1
n = (n + )h
0 (n + )2 0 e
2
2
where e is the anharmonicity constant.
The selection rule for an anharmonic oscillator is n = 0, 1, 2, . . . .