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1. The Q band in the vibrational spectrum of acetylene is observed in the [NET JUNE 2011]
(a) C–C stretching mode (b) C–H symmetric stretching mode
(c) Bending mode (d) C–H antisymmetric stretching mode.
2. In IR spectrum of [Co(CN)5H] the Co–H stretch is observed at 1840 cm–1. The (Co–D) stretching
3–

[Co(CN)5D]3– will appear at nearly [NET JUNE 2011]

–1 –1 –1 –1
(a) 1300 cm (b) 1400 cm (c) 1500 cm (d) 1600 cm .
14 –1
3. The rotational constant of N2 is 2 cm . The wave number of incident radiation in a Raman
spectrometer is 20487 cm–1. What is the wave number of first scattered stokes line (in cm–1) of 14N2?
[NET JUNE 2011]
(a) 20479 (b) 20475 (c) 20499 (d) 20495
4. The vibrational energy levels,  = 0 and ’ = 1 of a diatomic molecule are separated by 2143 cm–1. Its
n

anharmonicity (exe) is 14 cm–1, The values of e (in cm–1) and first overtone (cm–1) of this molecule
are respectively. [NET DEC 2011]
(a) 2143 and 4286 (b) 2157 and 4286 (c) 2157 and 4314 (d) 2171 and 4258
5. For a diatomic molecule AB, the energy for the rotational transition from J = 0 to J = 1 state is 3.9 cm–1.
The energy for the rotational transition from J = 3 to J = 4 state would be [NET JUNE 2012]
(a) 3.9 cm–1 (b) 7.8 cm–1 (c) 11.7 cm–1 (d)15.6 cm–1
6. For the vibrational Raman spectrum of a homonuclear diatomic molecule, the selection rule under
harmonic approximation is [NET JUNE 2012]
(a) v = 0 only (b) v = 1 only (c) v = 2 only (d) v = 0,  1
7. In the vibrational spectrum of CO2, the number of fundamental vibrational modes common in both
infrared and Raman are [NET DEC 2012]
(a) Three (b) Two (c) One (d) Zero
8. The relative population in two states with energies E1 and E2 satisfying Boltzmann distrubution is given
by n1/n2 = (3/2) exp [–(E1–E2)/kBT[. The relative degeneracy g2/g1 is : [NET DEC 2012]
(a) 2 (b) 2/3 (c) 3/2 (d) 3
9. The absorption spectrum of O2 shows a vibrational structure that becomes continuum at 56875 cm–1. At
the continuum, it dissociates into one ground state atom (O g) and one excited state atom (Oe). The
energy difference between Oe and Og is 15125 cm–1. The dissociation energy (in cm–1) of ground state
of O2 is : [NET DEC 2012]
56875 15125
(a) (b) (c) 72000 (d) 41750
15125 56875
10. The vibrational frequency and anharmonicity constant of an alkali halide are 300 cm–1 and 0.0025
respectively. The positions (in cm–1) of its fundamental mode and first overtone are respectively.
[NET DEC 2012]
(a) 300, 600 (b) 298.5, 595.5 (c) 301.5, 604.5 (d) 290, 580
11. In the presence of an external magnetic field (normal Zeeman effect), the transition 1D21P1 splits into:
[NET JUNE 2013]
(a) 9 lines (b) 8 lines (c) 7 lines (d) 6 lines
12. The equilibrium population ratio (nj/ni) of a doubly – degenerate energy level (Ej) lying at energy 2 units
higher than a lower non-degenerate energy level (Ej), assuming kBT = 1 unit, will be
[NET JUNE 2013]

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(a) 2e–2 (b) 2e2 (c) e2 (d) e–2

13. The atomic masses of fluorine and hydrogen are 19.0 and 1.0 amu, respectively (1amu = 1.67  10–27
kg). The bond length of HF is 2.0 Å. The moment of inertia of HF is [NET DEC 2013]
(a) 3.2  10 kg m (b) 6.4  10 kg m (c) 9.6  10 kg m (d) 4.8  10 kg m2
–47 2 –47 2 –47 2 –47

14. The C = O bond length is 120 pm in CO2. The moment of inertia of CO2 would be close to (masses of C
and O are 1.9  10–27 kg and 2.5  10–27 kg. respectively) [NET JUNE 2014]
(a) 1.8  10 kgm (b) 3.6  10 kgm (c) 5.4  10 kgm (d) 7.2  10 kgm2
–45 2 –45 2 –45 2 –45

15. Bond lengths of homonuclear diatomic molecules can be determined with the help of both
[NET DEC 2014]
(a) Rotational and vibrational spectroscopy.
(b) Rotational and rotational Raman spectroscopy.
(c) Rotational Raman and electronic spectroscopy.
(d) Vibrational and electronic spectroscopy.
16. If the component of the orbital angular momentum along the molecular axis of a heteronuclear diatomic
molecule is non-zero, the rotational –vibrational spectrum will show. [NET DEC 2014]
(a) P and R braches only (b) P and Q branches only
(c) Q and R braches only (d) All the P, Q and R branches
17. If the bond length of a heteronuclear diatomic molecule is greater in the upper vibrational state, the gap
between the successive absorption lines of P=branch [NET DEC 2014]
(a) Increases non-linearly (b) Decreases non-linearly
(c) Increases linearly (d) Decreases linearly
18. Intense band generally observed for a carbonyl group in the IR spectrum is due to [NET JUNE 2015]
(a) The force constant of CO bond is large
(b) The force constant of CO bond is small
(c) There is no change in dipole moment for CO bond stretching
(d) The dipole Moment change due to CO bond stretching is large.
19. The symmetric rotor among the following is [NET JUNE 2015]
(a) CH4 (b) CH3Cl (c) CH2Cl2 (d) CCl4
20. The spectroscopic technique, by which the ground state dissociation energies of diatomic molecules can
be estimated, is [NET JUNE 2015]
(a) microwave spectroscopy (b) infrared spectrocopy
(c) UV-visible absorption spectroscopy (d) X-ray spectroscopy
21. If the reduced mass of a diatomic molecule is doubled without changing its force constant, the
vibrational frequency of the molecule will be [NET DEC 2015]
1
(a) √2 times the original frequency (b) times the vibrational frequency
√2
(c) Twice the original frequency (d) Unchanged
22. The molecule with the smallest rotational constant (in the microwave spectrum) among the following is
[NET DEC 2015]
(a) N CH (b) HCCCl (c) CCl CF (d) B CCl
23. The spectroscopic technique that can distinguish unambiguously between trans-1, 2-dichloroethylene
and cis-1, 2-dichloroethylene without any numerical calculation is [NET DEC 2015]
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(a) microwave spectroscopy (b) UV-visible spectroscopy

(c) X-ray photoelectron spectroscopy (d) -ray spectroscopy
24. Upon application of a weak magnetic field, a line in the microwave absorption spectrum of rigid rotor
splits into 3 lines. The quantum number (J) of the rotational energy level from which the transition
originates is [NET JUNE 2016]
(a) 0 (b) 1 (c) 2 (d) 3
25. The correct statement in the context of NMR spectroscopy is [NET DEC 2016]
(a) Static magnetic field is used to induce transition between the spin state s
(b) Magnetization vector is perpendicular to the applied static magnetic field
(c) The static magnetic field is used to create population difference between the spin states
(d) Static magnetic field induces spin-spin coupling.
26. The rotational constant and the fundamental vibrational frequency of HBr are, respectively, 10 cm–1 and
2000 cm–1. The corresponding values for DBr approximately are [NET DEC 2016]
–1 –1 –1 –1
(a) 20 cm and 2000 cm (b) 10 cm and 1410 cm
–1 –1
(c) 5 cm and 2000 cm (d) 5 cm–1 and 1410 cm–1
27. Among the following, both microwave and rotational Raman active molecule is [NET DEC 2016]
(a) CH4 (b) N2O (c) C2H4 (d) CO2
28. The v = 0 to 1 vibration-rotation spectrum of a diatomic molecule exhibits transitions for R(0), R(1),
P(1) and P(2) lines at 2241, 2254, 2216 and 2203 cm–1, respectively. From this data, we can conclude
that the molecule [NET JUNE 2017]
(a) has rigid rotation and harmonic vibration (b) has anharmonic vibration
(c) has rotational-vibrational interaction (d) is affected by nuclear spin-statistics
29. The first electronic absorption band maximum of a polar and relatively rigid aromatic molecule appears
at 310 nm but its fluorescence maximum in acetonitrile solution appears with a large Stokes shift at 450
nm. The most likely reason for the Stokes shift is [NET JUNE 2017]
(a) large change in molecular geometry in the excited state
(b) increase in dipole moment of the molecule in the excited sate
(c) decrease in polarizability of the molecule in the excited state
(d) lowered interaction of the excited molecule with polar solvent
30. The molecule that will show Raman spectrum, but not IR spectrum, among the following is
[NET DEC 2017]
(a) H2 (b) HCl (c) BrCl (d) CS2
31. The normal mode of ethylene represented, by the figure below, is [NET DEC 2017]

(a) Only IR active (b) Only Raman active

(c) both IR and Raman active (d) neither IR nor Raman active
32. The pair that contains a spherical top and a symmetric top, among the following, is [NET DEC 2017]

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(a) CH4, CH2Cl (b) CH2Cl2, CH3Cl (c) CH3Cl, CH4 (d) CH4, C(CH3)4
33. In the pure Raman rotational spectrum of O2 , whose electronic ground state is 3𝑔− , transitions to/from
16

[NET JUNE 2018]

(a) Even J levels are missing (b) Odd J levels are missing
(c) All J levels appear (d) None of the J levels appear
34. A symmetric top molecule, among the following, is [NET JUNE 2018]
(a) Ethylene (b) Allene (c) butatriene (d) hexatriene
35. Assuming harmonic approximation, the energy change for the reaction HCl + D 2 → DCl + HD in cm-1
is (the vibrational frequency data in cm-1 is given in the table below), [NET JUNE 2018]
HCl D2 DCl HD
2885 2990 1990 3627
(a) -258 (b) +258 (c) -129 (d) +129
36. The transition moment integral for a rotational transition between J = 1; Mj = 0 and J = 2; Mj = 0 states
for a diatomic molecule along the z axis is proportional to [NET JUNE 2018]
 
(a) ∫0 𝑐𝑜𝑠 2  (3 𝑐𝑜𝑠 2  − 1)𝑑 (b) ∫0 𝑐𝑜𝑠 2  (3 𝑐𝑜𝑠 2  − 1) sin  𝑑
 
(c) ∫0 𝑐𝑜𝑠 (3 𝑐𝑜𝑠 2  − 1)𝑠𝑖𝑛 𝑑 (d) ∫0 𝑐𝑜𝑠 2  (3 𝑐𝑜𝑠 2  − 1) sin2  𝑑
37. A molecule AB2 shows the following IR and Raman spectra [NET DEC 2018]
–1
𝑣̅ (cm ) IR Raman
2215 vs, PR s, depol.
1250 vs, PR vs, pol.
560 s, PQR –
The structure of the molecule is
(a) Linear symmetruical (Dh) (b) Bent symmetrical (C2v)
(c) Linear asymmetrical(Cv) (d) Bent asymmetrical (Cs)
38. The third and fourth lines in the rotational Raman spectrum of CO are separated by 8 cm–1. The CO
bond length is given by [NET DEC 2018]
ℎ 3ℎ ℎ 5ℎ
(a) √162 𝑐 (b) √322 𝑐 (c)√322 𝑐 (d) √322 𝑐
1 1 2 
39. v = (𝑣 + 2)  − (𝑣 + 2) xe ; D = 4𝑥 [NET JUNE 2019]
𝑒
(a) 42044 (b) 84088 (c) 168175 (d) 336350
40. The populations of proton spins in the highest energy level of a sample in magnetic fields of 1.5 T and
𝑁′
7.0 T are N’ and N, respectively. The value of ln 𝑁 is (y, h, k, T are gyromagnetic ratio of the proton,
plank’s constant, Boltzmann constant and temperature of the sample, respectively; assume that the
partition functions for both systems can be approximated as 1) [NET JUNE 2019]
3 14
(a) 5.5 ħ/kT (b) ħ/kT (c) ħ/kT (d) 8.5ħ/kT
14 3
41. The rotational partition function is expected to be the smallest for the molecule, among the following,
[NET JUNE 2019]
(a) H2 (b) Li2 (c) N2 (d) F2
42. The correct statement about HCl and DCl, among the following, is [NET JUNE 2019]
(a) DCl has a smaller zero-point energy than HCl
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(b) HCl has a smaller vibration frequency than DCl

(c) The force constant k of the HCl bond is half that of DCl
(d) The reduced mass of DCl is smaller than that of HCl
43. The allowed transition in an atomic system is [NET JUNE 2019]
(a) F4 D3
3 3
(b) F4 D3
3 1
(c) F4 P4
3 3
(d) F4 D2
3 3

44. The frequency of O–H stretch occurs at  3600 cm . The O–D stretch frequency (in cm–1) would be
–1

close to [NET DEC 2019]

(a) 3000 (b) 2600 (c) 1800 (d) 900
45. In the pure rotational microwave spectrum of a XY molecule, the adjacent lines are separated by 4 cm–1.
If the molecules irradiated by a radiation of 30,000 cm–1, the first Stokes line (in cm–1) appears at
[NET DEC 2019]
(a) 29988 (b) 30012 (c) 30004 (d) 29996
46. For the d3 electron configuration. The ground state term symbol is [NET NOV 2020]
4 4 4 4
(a) F1/2 (b) F3/2 (c) F7/2 (d) F9/2
47. The equilibrium dissociation energy of a diatomic molecule is 4.75 eV and its stretching frequency
corresponds to 0.5 eV. The minimum energy required to dissociate the molecule in eV is
[NET NOV 2020]
(a) 4.75 (b) 4.25 (c) 4.50 (d) 5.00
48. The energy separation of 12C16O rotational energy levels between J” = 3 and J” = 9 is 24 cm–1. The
13 16 –1
rotational constant of C O in cm is closest to [NET NOV 2020]
(a) 2.98 (b) 0.88 (c) 1.90 (d) 2.08
49. The vibrational transition energies of a diatomic molecule corresponding to t’ = 1 t’ = 0 and 1= 2  t’
= 1 are 2143.1 cm–1 and 2116.1 cm–1 respectively. Theanharmonic constant (wexe) of the molecule in
cm–1 is [NET NOV 2020]
(a) 27 (b) 13.5 (c) 10 (d) 54
50. The number of micro states corresponding to the atomic term symbol 4 F is [NET FEB 2022]
(a) 7 (b) 12 (c) 28 (d) 42
51. The hypothetical NMR spectrum of 1H in 1H-C–2H would consist of (spin of the 2H is 1 ) a
[NET FEB 2022]
(a) singlet (b) Doublet of 1: 1 ratio
(c) Triplet of [Link] ratio (d) Triplet of [Link]
52. The molecule that will not absorb in the microwave region, but will absorb in the infrared is
[NET FEB 2022]
(a) N2 (b) C2H2 (c) HCl (d) H2O
53. The correct statements from the following set (i) to (iv) is [NET FEB 2022]
(i) If q is the displacement from equilibrium for harmonic motion, the potential energy is proportional to
q
(ii) If the vibrational frequency (𝑣̅ ) of HCl is 2990 cm–1, its zero point energy will be 1495 cm–1
(iii) The correct order of vibrational frequency of O –1H (X1), O–2H (X2), and O–3H(X3), is X1>X2> X3.
(iv) The fundamental vibrational transition of a diatomic molecule appears at 1880 cm–1. Its first
overtone will be at 940 cm–1
(assuminganharmonicity constant as zero).
(a) i, ii, iii only (b) i, ii, iii, iv (c) ii, iii only (d) i, ii, iv only
54. The following data is obtained for a light diatomic (AB) molecule from its rotational Raman
spectrum. [NET FEB 2022]
B = 2 cm–1 ;xe = 0.01 ; 𝑣̅𝑒 = 1600 cm–1.
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If the molecule is irradiated by a laser of 20, 000 cm–1, the expected Stokes lines (in cm–1) for this
molecule are
(a) 18348, 18356, 18368, 18380, 18388 (b) 18412, 18420, 18432, 18444, 18452
(c) 18380, 18388, 18400, 18412, 18420 (d) 18416, 18424, 18430, 18440, 18452
16 18
55. 1 mole of O2 and 1 mole of O2 in two different containers of the same volume have the same entropy.
Assuming there are no rotational and vibrational contributions of the entropy, if the temperature of 16O2 is
300K what is the temperature of 18O2 in K? [NET SEP 2022]

(a) 37.54 (b) 300.10 (c) 266.66 (d) 273.48

56. The vibrational energy of the nth state of HCl is approximately given as [NET SEP 2022]
1 1 2
G(n) = 3000 (𝑛 + 2) − 50 (𝑛 + 2) (in cm–1)
The vibrational quantum number, nmax, beyond which HCl undergoes dissociation is
(a) 29 (b) 59 (c) 119 (d) 19
57. For a C-H with a stretching frequency 3000 cm-1, what is the expected isotopes (deuterium) effect kH/kD at
298K for a full bond homolysis? Given h = 6.63x10-34Js, c=3x1010cm/s, kB=1.38x10-23 J/K.
[NET SEP 2022]
4 2
(a) e (b) 1 (c) e (d) e
58. The rotational absorption spectrum of H35Cl shows the following lines [NET SEP 2022]


̅ (𝑐𝑚−1 )
Neglecting centrifugal distortion, the value of the rotational constant in units of cm –1 is estimated as

(a) 3 (b) 5 (c) 10 (d) 20

59. Molecule B is twice as heavy as molecule A. The ratio of the thermal de Broglie wavelnegth of the
molecule A to that of the molecule B is [NET DEC 2023]
(a) √2 : 1 (b) 2 : 1 (c) 1 : 2 (d) 1 : √2
60. For a diatomic molecule, which is an annarmonic oscilimtor, ve (vibrational wavenumber) = 536.2
cm–1. The observed (𝑣̅ obs) value of fundamental frequency is 529.4 cm –1. The magnitude of 𝑣̅ obs (in
cm–1) for 3rd overtone is closest to [NET DEC 2023]
(a) 2076.8 (b) 1588.2 (c) 1567 (c) 1567.8 (d) 2117.2
61. Consider the nuclear shape of N7 and O8
14 17 [NET DEC 2023]
14N 17O
7 8
A Prolate Oblate
B Oblate Spherical
C Oblate Prolate
D Spherical Oblate
The option giving the correct shape, is
(a) A (b) B (c) C (d) D

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62. A schematic rotational-vibrational spectrum is depicted below and four lines of this spectrum for
two diatomicmolecules (M1 and M2) are tabulated. [NET DEC 2023]

If the reduced mass of M1 is 3-times that of M2, the ratio of bond length of M1 to that of M2 is
2 3 4 9
(a) (b) (c) (d)
3 2 9 4
63. In the rotational Raman Spectrum of a diatomic molecule, the energy gap between the first Stokes and
first anti-Stokes lines is [NET JUNE 2024]
[B : rotational constant]
(a) 6B (b) 4B (c) 12B (d) 8B

ANSWER KEY
1. C 2. A 3. B 4. A 5. D 6. B 7. D 8. B 9. D 10. B
11. A 12. A 13. B 14. D 15. C 16. D 17. A 18. D 19. B 20. B
21. B 22. C 23. A 24. A 25. C 26. D 27. B 28 C 29. B 30. A
31. B 32. C 33. A 34. B 35. C 36. B 37. C 38. A 39. C 40. A
41. A 42. A 43. A 44. B 45. A 46. B 47. C 48. C 49. B 50. C
51. C 52. B 53. B 54. B 55. C 56. A 57. D 58. A 59. A 60. A
61. A 62. A 66. C

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SOLUTION
1.
Ans. (c)
Sol. Q-band (or PQR contour) is obtained for the bending vibration of C 2H2 when its linearity is lost.
2.
Ans. (a)
1 𝑘
Sol. As Frequency of vibration = 2 √  ;
where k = force constant of bond
= reduced mass.
 Ratio of frequency/wave number of Co-D and Co-H bond is,
60 ×1
𝐶𝑜−𝐷
̅  1
= √𝐶𝑜−𝐷 = √ 60×2
61
≃
𝐶𝑜2𝐻
̅ 𝐶𝑜−𝐻 √2
62

1840

̅𝐶𝑜−𝐷 = 
̅𝐶𝑜−𝐻 / √2 = ≃ 1300 cm–1
√2
3.
Ans. (b)
Sol. In Raman Spectra, Stokes lines are separated by 4 B cm–1 and have wave number value less than the
incident radiation, but the first Stoke’s line is obsorbed at 
̅ − 6𝐵
 6B = 6  2 cm –1

Therefore, first Stoke line wave number = wave number of incident – 12cm–1 radiation.
= (20487 –12) cm–1 = 20475 cm–1
4.
Ans. (a)
Sol. 𝑣̅ 01 = 𝑒 (1-2xe)
or, 2143 cm–1 = e – 2exe or, 2143 cm–1 = e – 214 cm–1
ore = 2171 cm–1
First overtone more number is given by,
𝑣̅ 01 = 2𝑒 (1–3xe) = 2e – 6exe = 2  2171 – 6  14 = 4258 cm–1
5.
Ans. (d)
Sol. J = 0 to J = 1 appears at 2B = 3.9 cm–1.
Value of rotational constant B = 3.9/2 = 1.95
E = J=4 – J=3 = 20B–12B = 1.95  8 = 15.6 cm–1
6.
Ans. (b)
Sol. For a diatomic simple harmonic oscillator, all the vibrational energy levels are equally spaced and
selected rule
𝑣̅ = ±1only.
7.
Ans. (d)
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Sol. CO2 has center of symmetry so on per exclusion principle all the IR active vibration will be Raman
inactive. Hence, fundamental vibrational modes common in both IR/ and Raman will be zero.
8.
Ans. (b)
Sol. The relative population in two states with energy E1 and E2 satisfy Boltzmann distribution law,
[𝐸1−𝐸2 ]
𝑛1 𝑔
= 𝑔1 𝑒 𝑘𝐵 𝑇 ...(1) [where, g1 and g2 are degeneracy]
𝑛2 2
𝑛 3
Given :𝑛1 = (2) 𝑒𝑥𝑝 [–(E1–E2)/kBT] ....(2)
2
𝑔 3
Compare equation (1) and (2) , we get, 𝑔1 = 2
2
𝑔2 2
The value of 𝑔 = 3
1
9.
Ans. (d)
Sol.

Dissociation energy, Dg = 56875 – 15125 = 41750

10.
Ans. (b)
Sol. Given :e = 300 cm–1 and Xe = 0.0025 
Fundamental mode = e (1–2Xe
First overtone = 2e (1–3Xe)
Fundamental = 300 (1–2  0.0025) = 300 (1–0.0025) = 300  0.995 = 298.5
First overtone = 2×300 (1–3×0.0025) = 600(1–0.0075) = 595.5
11.
Ans. (a)
Sol. Selection rule, ML = 0,  1 (for Zeeman Effect) ML

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12.
Ans. (a)
Sol. kBT = 1
𝑛𝐽 𝑔𝑗 2
= 𝑒 −/𝑘𝐵 𝑇 = 1e–2 = 2e–2
𝑛𝑖 𝑔𝑖
13.
Ans. (b)
Sol. F atomic mass = 19.0 amu.
H atomic mass = 1 amu
H–F bond length = 2.0Å
𝑚 𝑚
I = r2, I = 𝑚 1+𝑚2 r2
1 2
19×1(𝑎𝑚𝑢)2 19
I= × 2.0 Å 2.0 Å = amu  2.0  2.0  Å2
20𝑎𝑚𝑢 2
19 ×1.67 ×10−27 𝑘𝑔 ×4
= × 10–10 10–10 m2
20
76 ×1.67 ×10−47
= kgm2 = 6.4  10–47 kgm2
20
14.
Ans. (d)
Sol. The moment of inertia of CO2.

I = 2mA R2
I = 2  2.5  10–27 kg  (120 pm)2
I = 2  2.5  10–27 kg  120  120  10–12 10–12 mtr2
I = 5  14400  10–51 kg mtr2
I = 72000  10–51 kg mtr2
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I = 7.2  10–47 kg mtr2

15.
Ans. (c)
Sol. Homonuclear diatomic molecules does not have any permanent dipole moment. So, it will not show
rotational spectra.
On the other hand, vibration does not make any changes in the permanent dipole moment of the
homonuclear diatomic molecule. So, it will not show vibrational spectra. But the homonuclear diatomic
molecules shows rotational Raman and electronic spectra and with the help of both, we can calculate the
bond length.
16.
Ans. (d)
Sol. For a heteronuclear diatomic molecule having non-zero component of orbit angular momentum along
the molecular axis, the energy levels of the vibrational rotational spectra will be
Evib–rot = Evib + Erot
1 1 2
= BJ(J+1) + (𝑣 + 2) 
̅ 𝑒 − 𝑥𝑒 (𝑣 + 2) 
̅𝑒 (in units of m–1)
Considering the transition from v = 0  v = 1
J = –1 will correspond to P branch
J = 0 will correspond to Q branch
J = 1 will correspond to R branch
17.
Ans. (a)
Sol. For a heteronuclear diatomic molecule, the energy levels of the virbrational rotational spectra will be
1 1 2
Evib–rot = BJ(J+1) + (𝑣 + 2) 
̅ 𝑒 − 𝑥𝑒 (𝑣 + 2) 
̅𝑒 (in units of m–1)
ℎ
Where, B = 82 𝐼𝑐 is the rotational constant of the molecule.
ℎ
 B = 82 𝑟 2𝑐
where ‘r’ is the bond length of the molecule.
If the bond length of the heteronuclear diatomic molecule is greater for upper vibrational state, the wave
number corresponding to the P-branch lines will be,
Evib–rot = 
̅ 𝑒 (1–2xe) – [2B + J’(B–B’) (J’+1)
where, J ' = rotational quantum number of upper vibrational state,
B' = rotational constant of upper vibrational state.
Gap between two successive P-branch lines is proportional to (4B–2B’)
As bond length r increases, B' decreases and gap between successive absorption line of branches
increases non-linearly.
18.
Ans. (d)
Sol. Intensity in IR spectrum is due to change polarity and change in dipole moment and expressed in term of
transition moment between two levels.
Transition moment, Rv = v’ v” d (transition moment in the form of dipole moment)
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Intensity, I = 〈𝑣′ "𝑣 〉2 (intensity in the form of dipole moment)

19.
Ans. (b)
Sol. Symmetric rotor is CH3Cl

Symmetric tops, IB = IC IA where, IA 0

The moment of inertia about the C–Cl bond axis is now not negligible because it involves the rotation of
three comparatively massive hydrogen atoms off this axis such a molecule spinning about this axis can
be imagined as a top and called symmetric top.
20.
Ans. (b)
Sol. The ground state energies of the atomic molecule can be estimated by infrared spectroscopy.

Illustration of dissociation
𝑣̅ 𝑐𝑜𝑛𝑡𝑖𝑛𝑢𝑢𝑚 𝑙𝑖𝑚𝑖𝑡 = D0” + Eex cm–1 (D0’ and 𝐷0" are dissociation energies)
21.
Ans. (b)
1 𝑘 1
Sol. ∵ v = 2 √  v  { = reduce mass}
√

𝑣2   1
= √1 = √21 = √2
𝑣1 2 1
1 1
 v2 = v1 times the original frequency.
√2 √2
22.
Ans. (c)
ℎ 1
Sol. B = 82 𝐼𝑐 B 𝐼 where, I = moment of inertia

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∵ I for Cl-C  C-F is highest

Therefore, B would be smallest for ClC CF
23.
Ans. (a)
Sol.

These two compounds are distinguished on the behalf of dipole moment by microwave spectroscopy
without any calculation.
24.
Ans. (a)
Sol. Under the selection rule, Mj = 0,  1

25.
Ans. (c)
Sol. In NMR spectroscopy the static magnetic field is used to create population difference between the spin
states.
26.
Ans. (d)
Sol. BHBr = 10 cm–1, 𝑣̅ 𝐻𝐵𝑟 = 2000 cm–1
𝐻𝐻𝐵𝑟 𝑣̅𝐻𝐵𝑟 1 2000 𝑐𝑚 −1
BPBr = and 𝑣̅ HBr = {∵ 𝐵  𝑎𝑛𝑑 𝑣̅ = }
2 √2  √
10 𝑐𝑚 −1 2000 𝑐𝑚 −1
 BPBr = = 5cm–1 and 𝑣̅ = = 1410 𝑐𝑚−1
2 √2
27.
Ans. (b)
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Sol. N2O is microwave and rotational Raman active molecule.

28.
Ans. (c)
Sol. Since, due to vibrational-rotational interaction P and R lines are obtained and molecule behave as a
diatomic vibrating rotor.
1 1 2
E = BJ (J+1) + (𝑣 + 2) 
̅ 𝑒 − (𝑣 + 2) 
̅ 𝑒 𝑥𝑒
29.
Ans. (b)
Sol. The first electronic absorption band maximum of a polar and relatively rigid aromatic molecule appears
at 310 nm but its fluorescence maximum in acetonitrile solution appears with a large stokes shift at 450
nm. The reason for stokes shift increasing dipole moment of the molecule in the excited state.
30.
Ans. (a)
Sol. H2 a homo diatomic molecule will have not changed in dipole moment. Thus, it will be IR inactive but
since H2 having polarisability in a Raman spectra. Thus, it will be Raman active.
31.
Ans. (b)
Sol. Only Raman active, (symmetric vibration, change in dipole moment is zero during vibration)
32.
Ans. (c)
Sol. Spherical top molecule  CH4 [Perfect geometry]
Ia = Ib = Ic
Symmetrical top molecule  CH3Cl Ia 0, Ib = Ic
33.
Ans. (a)
Sol. To make total wave function symmetric J=-levels must be antisymmetric Levels with odd J will be
present while levels with even J will be missing.
34.
Ans. (b)
Sol. The symmetric top molecule is allene.
35.
Ans. (c)
(𝐸𝐷𝐶𝑙 +𝐸𝐻𝐷 ) (𝐸𝐻𝐶𝑙 +𝐸𝐷2 )
Sol. E = −
2 2
1990+3627 2885+2990
=( )−( ) cm–1
2 2
−258
E = = −129 cm–1
2
36.
Ans. (b)
Sol. Y2n = (3 cos2–1) YLn = cos
 
P1,2 = "
∫0 𝑌2.0 𝑌 1,0cos sin d = ∫0 (3 𝑐𝑜𝑠 2  − 1)coscos sind

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
P1,2 = ∫0 𝑐𝑜𝑠 2  (3 𝑐𝑜𝑠 2  − 1) sin  𝑑
37.
Ans. (c)
Sol. Since, 2PR and 1PQR band Linear molecule.
Since, two of the vibrations are active in both IR and RAMAN asymmetric.
Hence, linear asymmetric (Cv)
38.
Ans. (a)
ℎ ℎ
Sol. Given : 4B = B cm–1 B = 2 cm–182 𝑟 2𝑐 = 2 cm–1 r = √82 𝑐 2

ℎ
= r = √162 𝑐
39.
Ans. (c)
1
Sol. Go + = Ev + 1 – Ev
2
1 1
Eo = (𝑣 + 2)w – (𝑣 + 2)2xew
3 3 2
Ev + 1 = (𝑣 + 2) 𝑤 − (𝑣 + 2) 𝑥𝑒 𝑤
3 1 3 2 1 2
Ev + 1 – Ev = (𝑣 + 2 − 𝑣 − 2) 𝑤 + [− (𝑣 + 2) + (𝑣 + 2) ] 𝑥𝑒𝑤
9 1
= w + [– 𝑣 2 − 4 − 3𝑣 + 𝑣 2 + 4 + 𝑣] 𝑥𝑒𝑤
= w + [–2–2v] xew
1
Gv + 2 = 𝑤 − 2𝑤𝑥𝑒 (1 + 𝑣)
y = c + mx
m = –2 wxe = –14 cm–1
wxe = 7
C = w = 2170 cm–1
2170 xe = 7
7
xe = 2170
𝑤 2170 ×2170
 = 4𝑥𝑒 = 4×7
 = 168175
40.
Ans. (a)
Sol. Energy of NMR transition
E = rħo
𝑁′ 𝑒 −𝑟ħ 1.5/𝑘𝑇
=
𝑁 𝑒 −𝑟ħ 7/𝑘𝑇
𝑁′
= 𝑒rħ/kT (7–1.5)
𝑁
𝑁′ 𝑟ħ
ln =  5.5
𝑁 𝑘𝑇
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41.
Ans. (a)
82 𝐼𝑘𝑇
Sol. qr = ℎ2
qr I r2
, qr
So, H2
42.
Ans. (a)
1 𝑘
Sol. v = 2𝜋 √𝜇

 , v
1
ZPE = 2 ℎ𝑣 , If v then, E
HCl<DCl
vHCl>vDCl
ZPEHCl>ZPEDCl
43.
Ans. (a)
Sol. Condition for allowed transition
(i) S = 0
(ii) L = 0,  1
(iii) J = 0,  1
3
F43D3
L =  1
S = 0
J =  1
44.
Ans. (b)
Sol. O–H v = 3600 cm–1
O–D v=?
1 𝑘 16 ×1 16
v = 2𝜋 √𝑢 1 (O–H) = 16+1 = 17
𝑣1  16 ×2 16 ×2
= √1 2(O–D) = 16+2 =
𝑣2 2 18

3600 16 ×2 17
=√ × 16v2 = 2619 cm–1
𝑣2 18

45.
Ans. (a)
Sol. In case of rotational spectra adjacent line gap = 2B
2B = 4cm–1 B = 2cm–1

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vstoke = vrayleigh – 6B
= 30, 000 – 6  2
= 29988 cm–1
46.
Ans. (b)
Sol.

1 3 3
L = 3 S = 3 2 = 2  2𝑆 + 1 = 2 2 + 1 = 4
(F)
3 6−3 3
L–S = 3– 2 = 2 = 2
Term symbol 2s+1LL-S = 4F3/2
47.
Ans. (c)
Sol. De = 4.75 eV (Equation dissociation energy )
we = 0.5 eV (stretching frequency)
Minimum energy required to dissociate the molecule =
De=Do+Eo

Do = De –Eo
= 4.75–0.25 = 4.5 ev
1 1
Ground state energy(ZPE) = 2 wo = 2 (0.5) = 0.25 𝑒𝑣

Morse Potential

48.
Ans. (c)
1
Sol. B 
𝐵𝐶13 𝑂16 𝐶12 𝑂16
=
𝐵𝐶12 𝑂16 𝐶13 𝑂16
1216
12
𝐶
𝑂16 ⇒
28
= 6.857 𝑔𝑚𝑜𝑙 −1 same unit
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13  16
13
𝐶
𝑂16 ⇒ = 7172𝑔𝑚𝑜𝑙 −1
29
Energy separation between 3rd line and 9th line in the spectrum
12B = 24 cm–1 B = 2 cm–1 (tan 12C 16O)
26.857
𝐵𝐶 13 𝑂16 = 7.142 cm–1 = 1.91 cm–1
49.
Ans. (b)
Sol. v=0v=1 E = we – 2wexe Anharmonic
v=1v=2 E = we – 4wexe Oscillator
1 1 2 𝑤𝑒 𝑤𝑒𝑥𝑒
E = (𝑣 + 2) we – (𝑣 + 2) we  e Eo = −
2 4
3 9
we – 2we xe = 2143.1 E1 = 𝑤𝑒 − 𝑤𝑒𝑥𝑒
2 4
5 25
we – 4we xe = 2116.1 E2 = 2 𝑤𝑒 − 𝑤𝑒𝑥𝑒
4
– + –
2 wexe = 27
27
wexe = 2 = 13.5 cm–1
50.
Ans. (c)
Sol. Term symbol 4F
2s + 1 = 4 L = 3 (for F)
No of microstates = (2s + 1) (2L+1)
= 4 (2  3 + 1)
= 7  4 = 28
51.
Ans. (c)
Sol.

52.
Ans. (b)
Sol. For microwave activity, molecule should possess permanent dipole moment.
Only homonuclear diatomic molecule are infrared active
N  N (both microwave & IR inactive)
H–CC–H (microwave inactive)
IR (active)
H–Cl (both microwave & IR active)
(both microwave & IR active)
Option B C2H2 correct
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53.
Ans. (b)
1
Sol. (i) PE = 2 kx2 v  x for SHO
–1
(ii) 𝑣̅ HCl = 2990 cm
1 1
ZPE = 2 𝑣̅ = 2 (2990) = 1495 cm–1
1
(iii) 𝑣̅ 
√𝑢
−1
𝑂1 𝐻(x1) 𝑂−2
2
𝐻 (x2) 𝑂−3
3
𝐻 (x3)
3>2>1 x1> x2> x3
(iv) Fundamental transition
̅e (1–2xe) = 1880 cm–1
𝑤
Given xe = 0 𝑤̅e = 1880 cm–1
̅e = 0
First overtone = 2𝑤 2we (1–3 xe) xe = 0
2𝑤̅e = 2  1880 = 3760 cm  940 cm–1
–1

Option A I, II and III are correct.

54.
Ans. (b)
Sol. B = 2cm–1xe= 0.01𝑣̅ e = 1600 cm–1
𝑣̅ exe = 20000 cm–1
For vibrational Rotational Raman :-
𝑣̅ stotes = 𝑣̅ exe – 𝑣̅ e (1–2 xe) = 20000 – 1600 (1–2  0.01)
= 18432 cm–1
𝑣̅ stokes = 𝑣̅ exe – 𝑣̅ e (1–2xe) + B (4J +6) J = 0(for J = 2–10)
= 20000 – 1568 + 2 (4  0 + 6) = 18444 cm–1
𝑣̅ stokes = 𝑣̅ exe – 𝑣̅ e (1–2xe)–B (4J + 6) J = 0(for J = 2–10)
= 20000 – 1568 – 2 (4 0 + 6) = 18420 cm–1
𝑣̅ stokes = 𝑣̅ exe – 𝑣̅ e (1–2 xe) + B (4J + 6) J = 1 (for J = 3–1)
= 20000 – 1568 + B(41+6) = 18452 cm–1
𝑣̅ stokes = 𝑣̅ exe – 𝑣̅ e (1–2xe) – B (4J + 6) J = 1
= 20000 – 1568 – 20 = 18412 cm–1(for J = 3–1)
55.
Ans. (c)
Sol. Formula of translation entropy
𝑉 2𝑚𝑘𝐵 𝑇 3/2 5
St = NkB[𝑙𝑛 {𝑙𝑛 ( ) + 2}]
ℎ2
SO16O2 = St of 18O2
2𝑚𝑂2 𝑘𝐵 𝑇16𝑂 3/2 2𝑚 𝑂2 𝑘𝐵 𝑇18𝑂 3/2
𝑉 2 𝑉 2
So, 𝑁 ( ) =𝑀( )
ℎ2 ℎ2
16 3/2
So, (m O2 𝑇16𝑂2 ) = (m O2 𝑇18𝑂2 )3/2 18

(32  300)3/2 = (36  T1802)3/2

(32 ×300)3/2
= (𝑇18𝑂2 )3/2
(36)5/2
𝑇18𝑂2 = 266.66
56.
Ans. (a)
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1 1 2
Sol. G(n) = 3000(𝑛 + 2) − 50 (𝑛 + 2) -------- (I)
1 1 2
G(n) = 𝑤𝑒 (𝑛 + 2) − 𝑤𝑒 𝑥𝑒 (𝑛 + 2) ---------(II)
Comparing eq (I) and (II), we get
we = 3000 cm-1
wexe = 50 cm-1
50
and so, xe = 3000 = 0.0167
1 1
nmax = 2𝑥 −
𝑒 2
Substituting the values,
1 1
nmax= − = 29.44  29
2×0.0167 2
57.
Ans. (d)
Sol. We know,
1 𝑘
𝑣̅ = 2𝑒 √ 
𝐻
𝑘𝐻 = 𝐴𝑒 −𝐸𝑎 /𝑅𝑇
𝑜
kD = 𝐴𝑒 −𝐸𝑎 /𝑅𝑇
𝐻
𝑘𝐻 𝑒 −𝐸𝑎 /𝑅𝑇
= 0
𝑘𝐷 𝑒 −𝐸𝑎 /𝑅𝑇
1
𝐸𝑎 = 2hv
𝑘 ℎ(𝑣𝐻 −𝑣𝐷 )
So, 𝑘𝐻 = 𝑒
𝐷 2𝑅𝑇
𝑘
v√
if force constant is almost same then,
𝐶−𝐻 12 12 12
= 13 × 7 = 7
 𝑐−𝐷
𝑣̅𝐶−𝐻
𝑣̅ 𝐶−𝐷 = 12 13
√ ×
7 12
3000
= 13
= 2201
√
7
𝑘𝐻 ℎ (6.626×10−34 )×(3000−2201)×(3×1010)
= 𝑒𝑥𝑝 (2𝑅𝑇 (𝑣 − 𝑣𝑒)] = 𝑒𝑥𝑝 [ ]
𝑘𝐷 2 ×(1.38×10−23 )×298
2
= 𝑒𝑥𝑝(1.13) e
58.
Ans. (c)
Sol. Rotational constant is the gap between the lines, i.e.
{(104.10 – 83.03) ≈ (124.30-104.10) ≈ (145.03 – 124.30)} = 20 on an average
So, 2B = 20
B = 10 cm–1
59.
Ans. (a)
Sol. According to Thermal De-Broglie wave length 
ℎ2
=√
2𝑚𝑘𝐵 𝑇
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1
So that   √𝑚
1
A  √𝑚 ------(1)
𝐴

1
B  √𝑀 --------(2)
𝐵

Given that MB = 2MA

Dividing equation (1) by equation (2)
𝐴 𝑀 2𝑀
= √𝑀𝐵 = √ 𝑀 𝐴 = √2
𝐵 𝐴 𝐴

 A : B = √2 : 1
60.
Ans. (a)
Sol. Vobs = ve (1–2xe) ––––––(A) fundamental absorption
 For 3rd overtone
vobs = 4ve (1–5xe) –-----(B)
vobs = ve (1–2xe)
529.4 = 536 (1–2xe) (∵ Given)
vobs= 529.4
ve = 536
 2xe = 0.012
xe = 0.006
Putting xe value in equation (B)
vobs = 4ve (1–5xe)
vobs = 4  536.2 (1–5  0.006)
vobs = 2076.8
61.
Ans. (a)
Sol. Moment of inertia along principal axis if mass of central atom more oblate other wise prolate.
62.
Ans. (a)
Sol. For rotational vibrational spectrum difference between two linos is 2B
For M1 For M2
2B1 = 1564 – 1540 2B2 = 1676–1644
2B1 = 24 2B2 = 32
B1 = 12 cm –1 B2 = 16 cm–1
For general
ℎ
B  82 𝐼𝐶
1
B𝐼

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𝐵 𝐼2  2
 𝐵1 = = 2 22 (I = 2)
2 𝐼 1 1
𝐵1 1 21
𝐵 =
2 2
2
2
16 32 21
 12 = (Given 1 = 32)
2 22
16 321
 12 = 22
21 16
 = 36
22
1 16 4 2
 =√ = =
2 36 6 3

63.
Ans. (c)
Sol. Concept :
In the rotation Raman spectrum of a diatomic molecule, three main types of lines are observed:
Rayleigh, Stokes , and anti-Stokes line. These line arise due to rotational transitions of the molecule
when it interacts with light. The rotational constant B is crucial in determining the positions of these
lines.
 Rayleigh Line : The Rayleigh line corresponds to the scattering of light without any change in
energy (elastic scattering). This line represents the incident photon energy and occurs at the same
wavelength as the incident light.
 Stokes Lines: In the Stokes process, the molecule absorbs energy from the incident photon and
transitions to a higher rotational energy level. The energy gap between the Rayleigh line and the
first stokes line is 6B.
 Anti-Stokes Lines: In the anti-Stokes process, the molecules loses energy by transitioning from a
higher rotational state to a lower state. The energy gap between the Rayleigh line and the first anti-
stokes line is 6B.
 Energy Gap Between First Stokes and First Anti-Stokes Lines: The total energy gap between the
first Stokes and first anti-stokes lines is the sum of the individual transitions, which results in 12B.
Explanation:
 The energy gap between the Rayleigh line and the first stokes or anti-Stokes line is calculated as :
E = 6B for both the Stokes and anti-Stokes lines.

The energy gap between the first Stokes and first anti-stokes lines is calculated as :
E = 12B, where B is the rotational constant.
 The gap between the Rayleigh line and both the first stokes and first anti-Stokes lines is 6B,
representing the transition the incident photon energy and the rotational transitions in the molecule.

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Conclusion :
The energy gap between the first Stokes and first anti-stokes lines in the rotational Raman spectrum
of a diatomic molecule is 12B.

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