A-31 Molecular Physics

1. The energy separation between two consecutive stokes lines in Raman Scattering
depends on

(a) Energy separation between vibrational levels in the excited state

(b) Wavelength of the incident light

(c) Energy separation between vibrational levels in the ground state

(d) Intensity of the incident light 2

2. Typical energy of the rotational modes in a polyatomic molecule like NH3 is:

(a) 106 eV (b) 103 eV (c) 104 eV (d) l eV

3. The vibrational constants 0 and 0 x0 of HCl are 2937.5 cm-1 and 51.6 cm-1. The first
Raman stokes line will be observed at (in cm-1)

(a) 2989.1 (b) 2885.9 (c) 2834.3 (d) 3040.7

4. Which one of the following molecules does not exhibit a rotational spectrum?

(a) H2 (b) CO (c) HCl (d) HBr

5. Infrared absorption can be observed in which of the following molecules?

(a) N2 (b) O2 (c) HCI (d) C2

6. The pure rotational levels of a molecule in the far-infrared region follows the formula
F(J) = BJ(J+1), where F(J) is the energy of the rotational level with quantum number J
and B is the rotational constant. The lowest rotational energy gap in rotational Raman
spectrum is:

(a) 2B (b) 4B (c) 6B (d) 8B

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7. Three values of rotational energies of molecules are given below in different units

P: 10 cm-1 Q: 10-23 J R: 104 MHz

Choose the correct arrangement in the increasing order of energy

(a) P, Q, R (b) R, Q, P (c ) R, P, Q (d) Q, R, P

8. Consider the pure rotational spectrum of a diatomic rigid rotator, The separation
between two consecutive lines ( v ) in the spectrum,

(a) Is directly proportional to the moment of inertial of the rotator

(b) In inversely proportional to the moment of inertia of the rotator

(c) Depends on the angular momentum

(d) Is directly proportional to the square of the interatomic separation

9. Light of wavelength 1.5 µm incident on a material with a characteristic Raman

frequency of 20 x 1012 Hz results in a stokes-shifted line of wavelength [Given : c = 3 x
108 m.s-1]

(a) 1.47 µm (b) 1.57 µm (c) 1.67 µm (d) 1.77 µm

10. In a Raman scattering experiment, light of frequency u from a laser is scattered by

diatomic molecules having the moment of inertia I. the typical Raman shifted frequency
depends on

(a) u and I (b) only u (c) only I (d) neither u nor I

11. For a diatomic molecule with the vibrational quantum number n and rotational quantum
number J, the vibrational level spacing En  En  En1 and the rotational level spacing
EJ  EJ  EJ 1 , are approximately

(a) En = constant, EJ = constant (b) En =constant, EJ  J

(c) En  n, EJ  J (d) En  n, EJ  J 2

12. In the microwave spectrum of identical rigid diatomic molecules, the separation
between the spectral lines is recorded to be 0.7143 cm-1. The moment of inertia of the
molecule, in kg m2, is :

(a) 2.3 x 10-36 (b) 2.3 x 10-40 (c) 7.8 x 10-42 (d) 7.8 x 10-46

14. Match the following:

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 P: Franck-Hertz experiment 1. Electronic excitation of molecules

Q: Hartree-Fock method 2. Wave function of atom

R: Stern-Gerlach experiment 3. Spin angular momentum of atoms

S: Franck-Condon principle 4. Energy levels in atoms

(a) (b) (c) (d)

P-4 P-1 P-3 P-4

Q-2 Q-4 Q-2 Q-1

R-3 R-3 R-4 R-3

S-1 S-2 S-1 S-2

15. The allowed rotational energy levels of a rigid hetero-nuclear diatomic molecule are
expressed as  J = BJ (J+1), where B is the rotational constant and J is a rotational
quantum number.

In a system of such diatomic molecules of reduced mass µ, some of the atoms of one
element are replaced by a heavier isotope, such that the reduced mass is changed to
1.05µ. In the rotational spectrum of the system, the shift in the spectral line,
corresponding to a transition J = 4  J = 5, is:

(a) 0.475 B (b) 0.50 B (c) 0.95 B (d) 1.0 B

16. A pure rotational Raman spectrum of a linear diatomic molecule is recorded using
electromagnetic radiation of frequency ve . The frequency of two consecutive stokes
lines are :

(a) ve – 10B, ve – 14B (b) ve – 2B, ve – 4B

(c) ve + 10B, ve + 14B (d) ve + 2B, ve + 4B

17. Which one of the following statement is INCORRECT in vibrational spectroscopy with
anharmonicity?

(a) The selection rule for vibrational spectroscopy is  v =  1,  2......

(b) Anharmonicity leads to multiple absorption lines

(c) The intensities of hot band lines are stronger than the fundamental absorption.

(d) The frequencies of hot band lines are smaller than the fundamental absorption.

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18. The separation between the first stokes and corresponding anti-stokes lines of the
rotational Raman spectrum in terms of the rotational constant, B is:

(a) 2B (b) 4B (c) 6B (d) 12B

19. In a diatomic molecule, the internuclear separation of the ground and first excited
electronic state are the same as shown in the figure. If the molecule is initially in the
lowest vibrational state of the ground state, then the absorption spectrum will appear as

(a) (b)

(c) (d)

20. Match the typical spectra of stable molecules with the corresponding wave-number
range

1. Electronic spectra i.106 cm-1 and above

2. Rotational spectra ii. 105-106 cm-1

3. Molecular dissociation iii. 100-102 cm-1

(a) 1 – ii, 2 – i, 3 – iii (b) 1 – ii, 2 – iii, 3 – i

(c) 1 – iii, 2 – ii, 3 – i (d) 1 – i, 2 – ii, 3 – iii

21. CO2 molecule has the first few energy levels uniformly separated by approximately 2.5
meV. At a temperature of 300 K, the ratio of the number of molecules in the 4 th excited
state to the number in the 2nd excited state is about.

(a) 0.5 (b) 0.6 (c) 0.8 (d) 0.9

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22. The rotational energy levels of a rigid diatomic molecule are given by E J = BeJ(J +1)
where J is the rotational quantum number and Be is the constant. The rotational
absorption spectrum of the molecules therefore consists of

(a) One resonance line

(b) Lines that are equally spaced.

(c) Lines where the spacing increases with frequency

(d) Lines where the spacing decreases with frequency.

23. The strongest three lines in the emission spectrum of an interstellar gas cloud are found
to have wavelengths 0 , 20 and 6 0 , respectively, where 0 is a known wavelength.
From this we can deduce that the radiating particles in the cloud behave like

(a) Free particles (b) Particles in a box

(c) Harmonic oscillators (d) Rigid rotators

24. Match the typical spectroscopic regions specified in Group I with the corresponding
type of transitions in Group II.

Group I Group II

(P) Infra-red region (i) electronic transitions involving valence

electrons

(Q) Ultraviolet- visible region (ii) nuclear transitions

(R) X – ray region (iii) vibrational transitions of molecules

(S)  – ray region (iv) transitions involving inner shell electrons

(a) (P,i); (Q, iii); (R, ii); (S,iv) (b) (P, ii); (Q, iv); (R,i); (S, iii)

(c) (P, iii); (Q,i); (R, iv); (S, ii) (d) (P.iv); (Q,i); (R, ii); (S, iii)

25. The first absorption spectrum of 12C16O is at 3.842 cm-1 while that of 13
C16O is at
3.673cm-1. The ratio of their moments of inertia is

(a) 1.851 (b) 1.286 (c) 1.046 (d) 1.038

26. The moment of inertia of a rigid diatomic molecule A is 6 times that of another rigid
diatomic molecule B. If the rotational energies of the two molecules are equal, then the
corresponding values of the rotational quantum numbers JA and JB are

(a) JA = 2, JB = 1 (b) JA = 3, JB = 1 (c) JA = 5, JB = 0 (d) JA = 6, JB = 1

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27. The spectral line corresponding to an atomic transition from J= 1 to J = 0 states splits in
0
a magnetic field of 1 kG into three components separated by 1.6 x 10 -3 A . If the zero
0
field spectral line corresponds to 1849 A , what is the g-factor corresponding to the J = 1
state?
hc
(You may use  2 104 cm )
0

(a) 2 (b) 3/2 (c) 1 (d) 1/2

28. Consider the hydrogen-deuterium molecule HD. If the mean distance between the two
atoms is 0.08 nm and the mass of the hydrogen atom is 938 MeV/c 2 then the energy
difference  E between the two lowest rotational states is approximately

(a) 10-1 eV (b) 10-2 eV (c) 2 x 10-2 eV (d) 10-3 eV

29. The two possible orientations of S with respect to an external magnetic field B along Z-
axis are

 1   1 
(c) cos 1    (d) cos 1   
1 1
(a) cos1    (b) cos 1   
 2  3  3  2

30. The magnitude of magnetic dipole moment corresponding to spin of an electron is

(a) µ B (b) 2µ B (c) √2µB (d) √3µB

31. A beam of electrons (each of rest mass m, charge e) enters in a uniform magnetic field B
along z-axis. The energy separation between the electrons having spin parallel and anti-
parallel with magnetic field, is
eB eB eB
(a) (b) (c) (d) 0
m 2m 4m

32. The angle between the orbital angular momentum and spin angular momentum for the
term 2D3/2 is

(a) 45° (b) 62° (c) 90° (d) 135°

33. Which of the following spectroscopic term is not allowed?

(a) 2D3/2 (b) 2F5/2 (c) 2P3/2 (d) 2D1/2

34. Which of the following statements is CORRECT?

The difference of spin-orbit correction to energy between the spin-down and spin-up
electron in a hydrogen like atom will

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 (a) increase with increase in atomic number.

(b) decrease with the principal quantum number

(c) increase with principal quantum number

(d) decrease with orbital quantum number

35. The electronic configuration of 25Mn atom is 1s22s22p63s23p63d54s2. The ground state
term of Mn atom will be

(a) 6S5/2 (b) 6P5/2 (c) 1S0 (d) 3P0

36. The ground state term of Mn3+ ion will be

(a) 5D0 (b) 5D4 (c) 6S5/2 (d) 6P5/2

37. Find the ground state term of the following atoms:

(a) 147 N (b) 126 C (c) 168 O (d) 1124 Na

(f) C  (g) Na 

38. The J = 0  J = 1 absorption line in CO occurs at a frequency of 1.153 x 1011s-1

(Given: The reduced mass of CO molecule is 1.14 x 10 -26 kg) The moment of inertia of
CO molecule is

(a) 0.8 x 10-46 kg - m2 (b) 1.5 x 10-46 kg – m2

(c) 0.8 x 10-42 kg - m2 (d) 1.5 x 10-42 kg –m2

The internuclear separation of CO molecule is

0 0 0 0
(a) 0.48 A (b) 0.84 A (c) 1.15 A (d) 1.95 A

39. The separation of lines in the far infrared spectrum of HCl is 20.68 cm-1.

(Given: The reduced mass of HCl molecule is 1.62 x 10-27 kg)

The J = 14  J = 15 transition occurs at

(a) 103.4 cm-1 (b) 206.8 cm-1 (c) 310.2 cm-1 (d) 413.6 cm-1

The moment of inertia of the HCl molecule is

(a) 1.34 x 10-40 kg – m2 (b) 2.7 x 10-40 kg – m2

(c) 1.34 x 10-47 kg - m2 (d) 2.7 x 10-47 kg –m2

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 The internuclear distance of HCl molecule is
0 0 0 0
(a) 0.48 A (b) 0.84 A (c) 1.30 A (d) 1.95 A

40. The wave numbers of the lines in a band are given by

v = 1000(2n – 1) for positive 'n'

= –1000(2n – 1) for positive 'n'

The moment of inertia of the emitter molecule of the spectrum is

(a) 2.8 x 10-49 kg – m2 (b) 5.6 x 10-49 kg – m2

(c) 8.4x10-49 kg – m2 (d) 11.2x10-49 kg – m2

41. The force constant of the bond in CO molecule is 1870 Nm-1.

(Given: The reduced mass of CO molecule is 1.14 x 10-26 kg)

The frequency of vibration of the CO molecule is

(a) 6.45 x 1013 s-1 (b) 9.45 x 1013 s-1 (c) 9.45 x 1011 s-1 (d) 6.45 x 1011 s-1

The energy of lowest vibrational level of CO molecule is

(a) 0.07 eV (b) 0.13 eV (c) 0.26 eV (d) 0.39 eV

The spacing between the vibrational enrgy levels of CO molecule is

(a) 0.07 eV (b) 0.13 eV (c) 0.26 eV (d) 0.39 eV 42

42. The force constant of the vibrating HCI molecule is 480 Nm-1. The amplitude of
vibration of HCl molecule in the first excited vibrational level will be

(Given: The reduced mass of HCl molecule is 1.62 x 10-27 kg)

0 0 0 0
(a) 0.19 A (b) 0.28 A (c) 0.42 A (d) 0.59 A

43. The vibrational frequency and the anharmonicity constant of HD molecule are 3817 cm-
1
and 95 cm-1 respectively. The zero point energy of HD molecule in the units of
kcal/mole, is

(Given: 1cm-1 = 2.858 x 10-3 kcal/mole)

(a) 1.25 (b) 2.47 (c) 3.39 (d) 5.39

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44. The fundamental band and the first overtone for CO molecule is centered at 2143.3 cm-1
and 4259.7 cm-1 respectively. (Given: The reduced mass of CO molecule is 1.14 x 10 -26
kg) The vibrational frequency of CO molecule is

(a) 2170 cm-1 (b) 2467 cm-1 (c) 1108 cm-1 (d) 3456 cm-1

The anharmonicity constant of CO molecule will be

(a) 6.8 cm-1 (b) 10.2 cm-1 (c) 13.5 cm-1 (d) 19.5 cm-1

45. The moment of inertia of the HCl35 molecule in the v = 0 and v = 1 levels is 20.8 x 10-7
kg – m2. The wave number difference between the R(0) and P(1) lines of the
fundamental band for HCl35 molecule is

(a) 4164 m-1 (b) 1041 m-1 (c) 2082 m-1 (d) 5205 m-1
0
46. In an experiment, the exciting line of of a sample is observed at 5460 A and stokes line
0
is observed at 5520 A . The wavelength of the anti-stokes line is
0 0 0 0
(a) 5420 A (b) 5401 A (c) 5380 A (d) 5580 A

47. In the vibrational Raman spectrum of HF molecule, the Raman lines are observed at
0 0
wavelengths 2670 A and 3430 A respectively. The fundamental vibrational frequency of
the molecule is

(a) 0.62 x 1014 Hz (b) 1.02 x 1014 Hz (c) 1.24 x 1014 Hz (d) 1.62 x 1014 Hz

48. In the Rotational Raman spectrum of HCl molecule, the displacements from the exciting
line are represented by

v   120  80 J  cm1

The moment of inertia of the molecule is

(a) 1.4 x 10-27 kg – m2 (b) 2.8 x 10-27 kg – m2

(c) 4.2 x 10-27 kg – m2 (d) 5.6 x 10-27 kg – m2

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