Find out the number of vibrational degrees of freedom of the

following compounds?
CH4, CO2, POCl3, H2O, NH3, SO2

Number of vibrational degrees of freedom

= 3N-6 for non-linear molecules
= 3N-5 for linear molecules
 What is the gross and specific selection rule for rotational
spectroscopy for a rigid rotator ?

Gross Selection Rule

Molecules having a permanent dipole moment only show rotational spectra

Specific Selection Rule

Transitions in which J changes by one unit are only possible, all other
transitions are spectroscopically forbidden

J  1
J  1 (absorption)
J  1 (emission )
 Which of the following diatomic molecules have a rotational
microwave spectrum: IF, O2 , KCl, Cl2

A pure rotational spectrum will be observed only for those

molecules that contain a permanent dipole moment.
Therefore, spectra will be observed only for IF and KCl.
Which of the following vibrational transitions will be observed for a
diatomic molecule (treated as a harmonic oscillator): v = 1 to v = 3; v =
2 to v = 3; v = 5 to v = 4.

The selection rules for vibrational translations is ∆v = ±1.

Therefore, the allowed transitions are v = 2 to v = 3; and v = 5 to v = 4.
Calculate the bond length of 12C16O using B=1.9302cm-1 and the
reduced mass is µ=1.14 x 10-26 kg
HCl is microwave active whereas H2 and Cl2 are microwave inactive,
justify.
During the rotational motion of HCl the direction of the dipole undergoes periodic
change resulting in fluctuations in the magnitude of a component of the dipole,
which is similar in form to the fluctuating electric field of radiation. Thus
interaction can occur, energy can be absorbed or emitted, and the rotation gives
rise to a spectrum .

Since H2 and Cl2 do not have a dipole moment, during their rotation they do not
generate any fluctuating electric field that is why they do not interact with
microwave and are micorwave inactive.
 What is the basic difference between the rotational spectra of a
rigid rotator and a non rigid rotator?

For a rigid rotator

 J  J 1  2 B (J  1 ) cm 1
Spectrum consists of equidistant (2B) lines

For a non rigid rotator

J  J 1  2 B (J  1 )  4 D ( J  1) 3
cm 1

The spectral lines are no longer equidistant

The separation decreases with increasing J value
 What are the factors that influence the intensity distribution
in a rotational spectrum?

Intensity depends on the population in each state.

Population of a state is governed by two factors:
1. Boltzmann distribution
2. Degeneracy in the energy state
The total relative population at an energy EJ  (2J + 1) exp(EJ /kT )

The population rises to a maximum and then diminishes.

The line intensities are directly proportional to the population
The first rotational line of 12C16O is found to occur at 3.8424 cm-1
while that of 13C16O at 3.6734 cm-1. Assuming the molar masses of
16O and 12C as 15.9994 g mol-1 and 12.000 g mol-1 respectively,

calculate the molar mass of 13C.

Given: 2B (12C16O) = 3.8424 cm-1 and 2B (13C16O) = 3.6734 cm-1

B12C16O  13C16O

B13C16O  12C16O
m13C m16O m12C  m16O M 13C ( M 12C  M 16O )
  
m13C  m16O m12C m16O M 12C ( M 13C  M 16O )
1.9212cm 1 M 13C (12.000  15.9994)
1

1.8367cm 12.000( M 13C  15.9994)

M13C = 13.0007 g mol-1 M = molar mass = mN

m = mass of one molecule (atom)
N = Avogadro Number
If a 5 x 10-6 M solution of anthracene in ethanol transmits 50%
of light at 360 nm, calculate the absorbance and the molar
absorption coefficient of anthracene in ethanol at the above
wavelength when the path length is 1 cm.
A certain substance in a cell of length ‘l’ absorbs 10% of the
incident light. What fraction of the incident light will be
absorbed in a cell five times as long.
Define Franck-Condon principle. Using a potential energy diagram
illustrate the possible transitions if 0  2 transition is the most
intense one.