CY6017 Optical and Magnetic Resonance Spectroscopy

Assignment 2 by K. Mangala Sunder

Department of Chemistry, Indian Institute of Technology Madras

Assume speed of light to be 3 x 108 m.s-1; Planck’s constant h = 6.626 x 10-34 J.s. Boltzmann
constant kB = 1.38 x 10-23 J.K-1
1. The SI unit for the moment of inertia of a diatomic molecule is
a. kg
b. N m-1
c. kg m2
d. Joule
2. The rotational constant for a diatomic molecule is given by the formula (I is the
moment of inertia about an axis passing through the centre of mass and
perpendicular to the bond axis)

h2
a.
8π 2 Ic
h
b.
8π 2 Ic
hIc
c.
8π 2
h2c
d.
8π 2 I
3. The spherical top molecule has the following relation between its moments of
inertia about the three principal axes which are mutually perpendicular to each
other,
a. Ix ≠ I y ≠ Iz

b. I=
x I y ≠ Iz

c.= y , Iz
I x I= 0

d. I=
x I=
y Iz

4. A linear molecule has only two rotational degrees of freedom because

a. there are only two non-zero moments of inertia in the point mass
approximation
b. two of the moments of inertia are equal and the third is very large
 c. all three moments of inertia sum to a constant and only two of them are
therefore independent
d. the sum of any two of them is equal to the third and therefore only two
need to be considered.
5. The molecule BF3 is planar and is a symmetric top. The following statement is the
correct statement,
a. The sum of two moments of inertia about the principal axes is equal to the
moment of inertia about the perpendicular axis.
b. One of its moments of inertia is zero
c. All three moments of inertia are unequal
d. All three moments of inertia are equal
6. The energy difference between successive rotational levels ( J and J + 1 ) in a rigid
diatomic molecule (in terms of its rotational constant B) is
a. hcB(2 J + 1)
b. 2hcBJ
c. 2hcB( J + 1)
d. hcB( J + 1)
7. The rotational levels of a rigid diatomic molecule with the quantum number J are
a. (2 J + 1) -fold degenerate
b. J -fold degenerate
c. doubly degenerate except for the quantum number K , projection of J
onto an axis, equal to zero
d. nondegenerate
8. The rotational constants of the two molecules HCl and DCl (Deuterium chloride) are
in the ratio, (assuming the equilibrium bond lengths to be the same)
BHCl µ HCl
a. =
BDCl µ DCl
BHCl µ DCl
b. =
BDCl µ HCl

BHCl µ HCl
2
c. = 2
BDCl µ DCl

BHCl µ DCl
2
d. = 2
BDCl µ HCl
9. The rotational constant for a certain molecule is 10 cm-1. The ratio of the number of
N1
molecules in J=1 to J=2 states at 300 K, is
N2
a. 1.4
b. 0.73
c. 1
d. 5
10. A molecule with the formula AB2 has a microwave spectrum with lines which are
equidistant. The structure of the molecule is ,
a. Linear A-A-B
b. Linear A-B-A
c. Bent A-B-B
d. Bent B-A-B:
11. The microwave spectrum of BF species has the following spectral data: J = 0 to J = 1,
96042.88 MHz for 10B19F. (Reference Source: NIST Tables.) The non-zero moment of
inertia is
a. 0.175 x 10-49 kg m2
b. 0.175 x 10-50 kg m2
c. 0.175 x 10-48 kg m2
d. 0.175 x 10-47 kg m2
12. The rotational spectrum of a symmetric top molecule is given by lines which are
separated from the neighboring ones by a spacing of ( J and K are rotational
quantum numbers for the initial state)
a. BJ ( J + 1)

b. BJ ( J + 1) − AK 2 where
c. 2B
d. B(2 J + 1)
13. Rotational levels of a symmetric top are degenerate and
a. the degeneracy is one for all values of K
b. the degeneracy is (2 J + 1)

c. the degeneracy increases as K 2 for each K

d. K = 0 state is nondegenerate and all others are doubly degenerate .
14. Only one of the following four tables is correct with respect to all entries. Identify
the correct table.
a.
CH4, CCl4, Octahedron Symmetric top
CHCl3, BH3, NH3 Spherical top
H2O, O3, CH2Cl2, C2H5Cl Asymmetric top
CO2, HC≡C-(C≡C)6-C≡H, HCN Linear
b.
CH4, CCl4, Octahedron Spherical top
CHCl3, BH3, NH3 Symmetric top
H2O, O3, CH2Cl2, C2H5Cl Asymmetric top
CO2, HC≡C-(C≡C)6-C≡H, HCN Linear
c.
CH4, CCl4, Octahedron Symmetric top
CHCl3, BH3, NH3 Asymmetric top
H2O, O3, CH2Cl2, C2H5Cl Symmetric top
CO2, HC≡C-(C≡C)6-C≡H, HCN Linear
d.
CH4, CCl4, Octahedron Asymmetric top
CHCl3, BH3, NH3 Spherical top
H2O, O3, CH2Cl2, C2H5Cl Symmetric top
CO2, HC≡C-(C≡C)6-C≡H, HCN Linear

15. The microwave spectrum of 12C16O has a rotational splitting (between adjacent
lines) of 115260 MHz. The carbon-oxygen interatomic distance is
a. 1.301 Angstrom
b. 1.403 Angstrom
c. 1.131 Angstrom
d. 1.0 Angstrom
16. The spacing between adjacent microwave lines for the molecule 16O-12C-32S is 12.16
GHz. The transition frequency corresponding to the transition between J = 20 and J =
21 is
a. 276.52 GHz
b. 255.36 GHz
 c. 243.20 GHz
d. 222.04 GHz
17. The spacing between adjacent microwave lines for the molecule 16O-12C-34S is 11.86
N2
GHz. The ratio of the number of molecules in the J = 2 to J = 3 state, , is
N3
N2
a. = 1.33
N3
N2
b. = 1.0
N3
N2
c. = 0.718
N3
N2
d. = 0.864
N3
18. Using figure 1 given below, the moment of inertia of water molecule about the z
axis is obtained as

Figure 1

a. mH r 2 sin 2 θ

θ
b. 2mH r 2 sin 2
2
2θ
c. mH r 2 sin
2
θ
d. 2mH r 2 cos 2
2
19. The rotational J value for which the intensity of transition will be maximum is given
by the value
a. J = 0 , lowest rotational state
b. J = 1 , the first non-trivial rotational state.
 k BT 1
c. J
= − or the nearest integer.
2hcB 2
hcB
d. J= or the nearest integer
k BT
20. The rotational constant of 12C16O is 3.842 cm-1 and that of 13C16O is 3.673 cm-1. The
ratio of constants, given by 1.046, is consistent with the ratio
µ 12
C16 O
a.
µ 13
C16 O

µ 13
C16 O
b.
µ 12
C16 O

2
 µ13 C16O 
c.  
 µ12 C16O 
2
 µ12 16 
d.  C O 
 µ13 C16O 

Long Problems:

1. Draw the rotational energy level spectrum of the following two molecules in their
ground vibrational state, from J= 0 to J = 3 assuming that the rotational motion is
that of a rigid top. Where necessary use the tables given in the book by Peter
Bernath for the energy levels if they are asymmetric tops.
a. Ozone with molecular rotational constants A=3.55 cm-1, B = 0.4425 cm-1 and
C=0.39 cm-1
b. Deuterated Methane CH3D with Rotational Constants A = 5.260 cm-1, B =
3.890 cm-1 and C = 3.890 cm-1.
c. BF3 with D3h symmetry and with B-F bond length 1.310 Å. (Calculate A, B and
C!)

2. Obtain the eigenvalues and eigenfunctions for a non-rigid rotor molecule whose
rotational Hamiltonian has the form
H Rot  BJ 2  ( A  B) J z2  J J 4  JK J 2 J z2  K J z4 . A, B and all Delta are
constants.

3. Evaluate the following:

a.  J x ,[ J y , J z ]   J y ,[ J z , J x ]   J z ,[ J x , J y ]
     
b.  A,  B, C    B, C , A  C ,  A, B  where A, B and C do not commute with
each other. It is also known as Jacobi identity.
c.  J ,  J J  J J 
 z  x y y x  
d.  J ,  J J  J J 
 z  x y y x  