CH-442 Molecular Spectroscopy End-Semester Exam 22/04/2015

Answer any 10 Questions Maximum Marks 50

Note: If you answer MORE than 10 Questions, only the FIRST 10 will be corrected

1. a) What is a Hermitian operator? [1]

b) What is normal mode? [1]
c) Can a harmonic oscillator ever be dissociated? [1]
d) Express the potential ‘V’ as power series in displacement ‘q’ and identify the force [1]
constant.
e) What should be the direction of the oscillating electric field to bring about transition [1]
between energy levels of a particle-in-a-box along the x-axis?

2. a) The rotational constants for 1H35Cl are 10.44 and 10.14 cm-1 in   0 and   1 states, [1]
respectively. Explain.
b) For CO2 only three vibrations at 667, 1340 and 2349 cm-1 are observed. Explain. [1]
c) Is it possible to record pure rotational spectrum of PCl 3? [1]
d) What happens to the polarization selection of electronic transitions when benzene is [1]
substituted?
e) The rotation-vibration coupling is usually very small and can be neglected. Why? [1]

3. a) Evaluate the commutator r, H  [2]

b) Write down the dipole expansion. Explain the first three terms and their relevance [2]
in various spectroscopic techniques.
c) The Δs≠0 transitions are very weak. Why? [1]

4. a) The vibrations of AB2 molecule span 2A1+B2 representation of C2v point group. Which [2]
of these vibrations are (i) Infrared active and (ii) Raman active. Why?
b) List the number of possible states for the one electronic transition of O2 molecule [2]
from HOMO to LUMO.
c) What does triplet mean? [1]

5. a) In an NMR experiment the static magnetic field B0 is applied along the z-direction. [3]
Show that the NMR transitions are polarized along x,y – axes.
b) The rotational energy for prolate  I a  Ib  I c  and oblate  I a  Ib  I c  are given by [2]
2
 1 1  2
 1 1 
Erot ( p)  J  J  1 K 
2 2
  and Erot (o)  J  J  1  K2 2   .
2Ib  2I a 2Ib  2Ib  2I c 2Ib 
Sketch the energy level pattern as a function of J and K quantum numbers.

6. a) Given Beff(A) > Beff(X) and JAX is the coupling between A and X. Draw the energy level [2]
diagram for the AX spin system and illustrate all the allowed transitions.
b) In a NMR experiment, what would be difference in population for a fivefold increase [1]
in the static magnetic field?
c) How the 0-0 transition is determined using absorption and emission spectra? [1]
d) What is difference between homogeneous and in-homogeneous linewidths? [1]
 7. a) The spacing between first two vibrational levels of CO molecule is 2170 cm-1. Taking [2]
the mass of C to be 12 amu and O to be 16 amu compute the effective spring constant
k. (1 amu = 1.66 × 10-27 kg)
b) Evib    1 2  h e    1 2  xe h e For 1H79Br  e =2650 cm-1 and the xe e =45 cm-1. [3]
2

Find the fundamental and first overtone for 1H79Br, 2H79Br and 1H80Br.

8. a) What is the direction of polarization of the n→π* transition of a localized carbonyl [4]
group in a ketone?
b) The rotational selection rules are usually ignored for electronic transitions of the [1]
polyatomic molecules. In such case what is the numerical value of the integral
 M 
YM J 
Y Jd  rot

9. a) Show that sum of Franck-Condon factors is unity. [2]

b) The bond length of CO is 1.13 and 1.37 Å in the ground and excited states, [2]
respectively, and the corresponding vibrational frequencies ( e ) are 2170 and 1180
cm-1. Sketch the Franck-Condon profile of the CO absorption band.
c) How is the 0-0 transition determined using absorption and emission spectra [1]

10. A metal ligand complex ML4 has square planar structure. Evaluate the symmetry of all [5]
the normal modes.

11.
a) The molecular orbital picture of the H2O with (y,z) being molecular plane [3]
is given. Evaluate properties of the transition in which the electron is
promoted from the HOMO to LUMO (allowed or not and the direction of
polarization).

b)Would the nature of the electronic transition change if one of the [1]
hydrogens in water molecule is substituted by deuterium?

c) The valance electronic configuration of SO2 molecule is [1]

(1a2)2(4b2)2(6a1)2(2b1)0. Comment the electronic transition from HOMO to
LUMO.

12. a) In a NMR experiment the static magnetic field is applied along the z-axix. Show that [3]
the NMR transition are only allowed in the (x,y) plane with ΔMz=±1.
b) Classify the following molecules into spherical, symmetrical and asymmetrical rotors [2]
(i) 1,4-Difluorobenzene, (ii) Boric acid, (iii) iron carbonyl, (iv) cyclohexane, (v) nickel
carbonyl (vi) s-triazine.

*****End-of-Question-Paper*****
***************************************************************************

Character table for C2v point group

linear,
E C2 (z) σv(xz) σv(yz) Quadratic
rotations
A1 1 1 1 1 z x2, y2, z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz

Multiplication table for C2v point group

A1 A2 B1 B2
A1 A1 A2 B1 B2
A2 A2 A1 B2 B1
B1 B1 B2 A1 A2
B2 B2 B1 A2 A1

Character table for D4h point group

linears,
E 2C4 (z) C2 2C'2 2C''2 i 2S4 σh 2σv 2σd quadratic
rotations
A1g 1 1 1 1 1 1 1 1 1 1 x2+y2, z2
A2g 1 1 1 -1 -1 1 1 1 -1 -1 Rz
B1g 1 -1 1 1 -1 1 -1 1 1 -1 x2-y2
B2g 1 -1 1 -1 1 1 -1 1 -1 1 xy
Eg 2 0 -2 0 0 2 0 -2 0 0 (Rx, Ry) (xz, yz)
A1u 1 1 1 1 1 -1 -1 -1 -1 -1
A2u 1 1 1 -1 -1 -1 -1 -1 1 1 z
B1u 1 -1 1 1 -1 -1 1 -1 -1 1
B2u 1 -1 1 -1 1 -1 1 -1 1 -1
Eu 2 0 -2 0 0 -2 0 2 0 0 (x, y)