Rotational Spectra Vibrational Spectra

The expression for the rotational energy

levels is given by:

+ , where J=0,1, 2

The expression for the rotational energy levels
is given by:

= +

, = , , , ____
The spacing between the adjacent rotational
levels become far apart with the increase of
the rotational quantum number
The spacing between the adjacent vibrational
levels are equal.
The transition between adjacent rotational
energy levels result in radiation that lies in the
microwave range of frequencies (f~10
9
Hz)
The vibrational transition photons of a
diatomic (or linear) molecule lie in the infrared
region of the spectrum(f~10
11
Hz)
The energy separation between successive
rotational level is much smaller than the
separation between successive vibrational
levels. This means that at ordinary
temperature most molecules are in =0
vibration state with zero point energy, but
these molecules can be in various rotation
states.
At room temperature, most of the molecules
have vibrational energies corresponding to the
=0 state i.e. vibrational transitions are
forbidden at room temperature. This is
because the spacing between vibrational
states is much greater than the thermal energy
(k
B
T) at room temperature.
Molecular Spectra
Absorptive transitions between
the v = 0 and v = 1 vibrational states
of a diatomic molecule.
Expected lines in the absorption
spectrum of a molecule. These same
lines appear in the emission spectrum.
Total energy of a molecule :
Problem-1: The moment of inertial of the CO molecule is 1.46x10
-46
kg-m
2
.
Calculate the energy in eV and the angular velocity in the lowest rotational
energy level of the CO molecule.
Ans: E=7.6x10
-23
J or, 4.75 x 10
-4
eV

= 10.2 x10
-11
rad/sec
Hint: The Lowest rotational energy level will be J=1 state

Because for J=0, E
J
= 0 and the minimum molecular energy is vibrational
Problem-2: In the near infra-red spectrum of HCl molecule there is single
intense band at 2885.9 cm
-1
[wave number]. Assuming that it is due to the
transition between the vibration levels, show that the force constant k is
480Nm
-1
(Given M
H
= 1.68 x 10
-27
kg)
Problem-3: The force constant of the bond in CO molecule is 187 Nm
-1
.
Calculate the frequency of vibration of the molecule and the spacing
between its vibrational energy levels in eV. Given that the reduced mass
of CO=1.14x10
-26
kg: h=6.6 x 10
-34
Js and 1eV= 1.60x10
-19
J.
Ans. = 2.04x 10
-13
Hz

E = 8.44 x10
-2
eV