16.03.

2016
 The rigid rotor model
The Schrodinger expression
Application
References
 A diatomic molecule having mass m1 and m2; m1> m2
The centre of mass lies close to the atom having higher
mass.
r1 is the distance between centre of mass and the
heavier atom and r2 is the distance between centre of
mass and lighter atom.
Both the atoms rotate around the centre of mass with
some fixed frequency which is the rotational
frequency.
Let l be the distance between the two atoms which in
chemical terminology is known as the bond length.
The bond length remains rigid throughout the rotation
Kinetic energy is given by-

Since v = r
Therefore :
 The classical kinetic energy of the rigid rotator can be
written as :

The potential energy term is zero and therefore the total energy is equal
to the kinetic energy :

or
 Replacing the with corresponding quantum
mechanical operators , we have :

The Schrodinger equation for the rigid rotor is

 It is customary to define a rotational constant B
for the molecule

so that the solutions for the energy states of a

rigid rotator can be expressed as
 In many cases the molecular rotation spectra of
molecules can be described successfully with
the assumption that they rotate as rigid rotors.
In these cases the energies can be modelled in a
manner parallel to the classical description of
the rotational kinetic energy of a rigid object.
From these descriptions, structural information
can be obtained (bond lengths and angles). The
most straightforward examples are those of
diatomic molecule
 BOND LENGTH OF HCl

A bond length for the HCl molecule can be calculated

from the HCl spectrum by assuming that it is a rigid
rotor and solving the Schrodinger equation for that
rotor.
For a free diatomic molecule the Hamiltonian can be
anticipated from the classical rotational kinetic energy

and the energy Eigen values can be anticipated from

the nature of angular momentum.
 Assuming that the bond length is the same for
the ground and first excited states, the
difference between the j=1,v= 0->j=0, v=1
transition and the j=0, v=0->j=1,v=1 transition
frequencies can be used to estimate the bond
length. The separation between the two
illustrated vibration-rotation transitions is
assumed to be twice the rotational energy
change from j=0 to j=1.
 Substitution of numerical values leads to an
estimate of the bond length r:
 This compares reasonably with the value
r=.127 nm obtained from pure rotational
spectra
 https://en.wikipedia.org/wiki/Rigid_rotor
http://hyperphysics.phy-astr.gsu.edu/
A textbook of physical chemistry volume 4 by
K L Kapoor