CH-442 Molecular Spectroscopy Mid-Semester Exam

Max Marks-25 22/02/2014 Time: 2Hrs

1A. From the solution of classical wave equation arrive at the operator corresponding to energy [3]
and momentum.

Under the influence of electromagnetic field show that Hamiltonian is given by [2]
1B.
H ˆ0  i q A
ˆ H ˆ
m

2. For an n-state system under the influence of a time-dependent perturbation, show that the [5]
1
time dependent coefficients are given by cm (t ) 
i
 c (t ) e
n
n
 inmt ˆ (t ) n
mH

3A. The Strickler-Berg paper establishes the relationship between the absorption band (through [3]
molar extinction coefficient) and lifetime of the excited state. Given the following data,
estimate the ratio of lifetimes of perylene and rubrene.

  ( )ln d( )  f 3
1
2
av

Perylene 3.320 0.948 2.289

Rubrene 1.38 0.480 2.244

Explain using dipole expansion, the origin of selection rules for rotational, vibrational and
3B [2]
Raman spectroscopic methods

4A. Considering all the other factors to be equal, what will be the ratio of Einstein ‘A’ coefficient [2]
for the rotational transition at 2 GHz and electronic transition at 400 nm.

4B. What are homogeneous and in-homogeneous linewidths? What factors contribute to the [2]
linewidths?

4C. What is the difference between the two integrals f ˆ   i and i ˆ   f ? [1]

5A. Explain each term and its significance in the Fermi Golden rule. [2]
2
2 2 E 2
w fi  2   ( E fi ) where   0
2
f ˆ  i
4

5B. Suitably modify the equation given in question 2 to evaluate the time dependent coefficient [3]
of a final state f starting from an initial state i using first order correction to in the
time-dependent perturbation theory. Justify the usage of first order correction.

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