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Objective Questions (Atomic and Molecular Physics)

Q1. How many revolution does an electron in the n = 2 state of hydrogen atom makes
before dropping to n = 1 state? The average life time of an excited state is 10-8 second.
(a) 8.1 x 1014 s-1
(b) 8.2 x 106 s-1
(c) 8.0 x 1015 s-1
(d) 8.3 x 107 s-1
Q2. The positronium atoms is a system that consist of a positron and an electron that

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orbit each other where me+ = me-. While when a proton capture muon (μ -). It forms the
muonic hydrogen atom, where m   207 me . Which of the following statement is not

true for these atoms for n = 1?

(a) The radius of positronium atom is twice as large as it is for ordinary hydrogen atom.
(b) The energy of positronium atom is half as it is for ordinary hydrogen atom.
(c) The muonic hydrogen atom is 186 times smaller than ordinary hydrogen atom.
(d) The ionization energy of muonic atom is 186 times smaller than ordinary hydrogen
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atom.
Q3. The finite nuclear mass causes a slight variation in the Rydberg constant (R) from
atom to atom. If RH and RHe is Rydberg constant for hydrogen and Helium, the ratio RH :
RHe is (MH & me mass of hydrogen nucleus and electron)
4 M H  me 4 M H  me
(a) (b)
4M H  me  M H  me
M H  me 4M H  me 
(c) (d)
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4 M H  me 4 M H  me
Q4. If R1 is Rydberg constant of ordinary hydrogen atom and R2 is Rydberg constant of
positronium atom, which of the following is the correct relation?
(a) R1 = R2 (b) R1 = 2R2
(c) 2R1 = R2 (d) R1 = 3R2

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Q5. If λB and λp is the wavelength of the series limit of Bracket and Pfund series
respectively. The ratio of λB and λp will be
16 25
(a) (b)
25 36
9 9
(c) (d)
25 16
Q6. An electron collides with a hydrogen atom in its ground state and excites it to a state
of n  3 . How much energy was given to the hydrogen atom in this inelastic collision?

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(a) 13.6eV (b) 6.8eV (c) 12.1eV (d) 1.51eV
Q7. A muon is an unstable elementary particle whose mass is 207 me and whose charge

is e . A proton captures a μ- to form a muonic atom. The ionization energy of the atom is
(a) 6.8 eV (b) 2.5 eV (c) 250 eV (d) 2.5 keV
Q8. Electron beam enters a uniform magnetic field of 1.0Tesla. The energy difference
electrons whose spins are parallel and antiparallel to the field is
(a) 1.01 x 10-3 eV (b) 1.16 x 10-4 eV
(c) 1.31 x 10-5 eV (d) 1.51 x 10-2 eV
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Q9. The fine structure of atomic spectral lines arises because of
(a) Interaction between electron spin and nucleus spin
(b) Interaction between electron – electron spin
(c) Interaction between electron-electron orbital angular momentum
(d) Interaction between electron spin and orbital angular momentum.
0
Q10. The spin-orbit effect split the 3P  3s transition in Sodium into two lines, 5890 A
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0
corresponding to 3P3/ 2  2 S1/ 2 transition and 5896 A corresponding to 3P1/2 → 3S1/2

transition. Using these wavelength, what is the effective magnetic field experienced by
the outer electron in the sodium atom as a result of its orbital motion?
(a) 18.5T (b) 6.3T (c) 9.8T (d) 2.3T

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Q11. The magnetic moment of an atom in the state 3Po is

(a) 3 (b) 2
(c) 1 (d) 0
Q12. Which of the following statement regarding Lamb shift is correct?
(a) The Lamb shift is caused by Thomas precession
(b) Lamb shift causes splitting between the 1s and 2s energy levels in hydrogen.
(c) The Lamb shift is caused by vacuum fluctuations of the electromagnetic field.
(d) Lamb shift causes splitting between 22P3/2 and 2 2S1/2.

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Q13. The fine structure of atomic spectral lines arises because of
(a) Interaction between electron spin and nucleus spin
(b) Interaction between electron – electron spin
(c) Interaction between electron-electron orbital angular momentum
(d) Interaction between electron spin and orbital angular momentum.
Q14. The spectroscopic terms for Carbon (Z=6) are 1So; 3P2,1,0; 1D2. According to Hund’s
which of the following correctly represent the order of energy of the states?
(a) 3Po > 3P1 > 3P2 > 1D2 > 1So
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(b) 3P2 > 3P1 > 3Po > 1D2 > 1So
(c) 1So > 1D2 > 3P2 > 3P1 > 3Po
(d) 1So > 1D2 > 3Po > 3P1 > 3P2
Q15. The spectroscopic terms for oxygen (Z = 8) are same as of Carbon and they are
1
So, 3P2,1,0, 1D2. Which of the following orders is correct according to Hund’s rule?
(a) 1So > 1D2 > 3Po > 3P1 > 3P2
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(b) 1So > 1D2 > 3P2 > 3P1 > 3Po
(c) 3Po > 3P1 > 3P2 > 1D2 > 1So
(d) 3P2 > 3P1 > 3Po >1D2 > 1So
Q16. The electronic configuration of Nitrogen (Z=7) is 1s2 2s22p3, which gives rise to
2 o
P 1/2, 2Po3/2, 2Do3/2, 2Do3/2 & 4So3/2 spectral terms. The ground state spectral terms is
(a) 2Po1/2 (b) 2Po3/2
(c) 4So3/2 (d) 2Do5/2

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Q17. The ground state of hydrogen atom (1 2S1/2) is split by the hyperfine interaction
between two levels F = 0 and F = 1.
(i) State F = 0 is ground state while F = 1 is excited state.
(ii) State F = 1 is ground state while F = 0 is excited state.
Which of the following is correct?
(a) only (i) is true
(b) only (ii) is true
(c) (i) is always true but (ii) is also true in some cases.

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(d) (ii) is always true but (i) is also true in some cases.
Q18. The doublet splitting of the first excited state 2P3/2 → 2P1/2 of H is 0.365 cm-1. The
corresponding splitting in wave number for Li2+ is
(a) 81 cm-1 (b) 29.6 cm-1
(c) 1.85 cm-1 (d) 0.365 cm-1
Q19. The ground state electronic configuration of Neon is 1s2 2s2 2p6. In the lowest
excited state, one electron from 2p move into 3s orbital. In excited state which of the
following is not the possible value of (L, S, J)?
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(a) 1, 1, 2 (b) 1, 1, 1 (c) 1, 1, 0 (d) 1, 2, 1

Q20. Singly ionized Cr  has electronic configuration of 1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 5 . The

ground state spectral term of Cr  is

(a) 1 S0 (b) 6 S5 / 2 (c) 3 S1 (d) 5 S3 / 2

Q21. A sample of a certain element is placed in a 0.3T magnetic field and suitably
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excited. How apart are the Zeeman components of the 450 nm spectral line of this
element?
0 0 0 0
(a) 0.28 A (b) 0.028 A (c) 0.0028 A (d) 2.8 A

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Q22. The number of Zeeman component for 1F3 → 1D2 is

(a) 15 (b) 12
(c) 6 (d) 3
Q23. The number of Zeeman component for 2P3/2 → 2S1/2 transition is
(a) 6 (b) 3
(c) 8 (d) 12
Q24. The numbers of Zeeman components for 2D3/2 → 2P1/2 transition are
(a) 3 (b) 6

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(c) 9 (d) 12
Q25. The numbers of Zeeman components for 2D5/2 → 2P3/2 transition are
(a) 3 (b) 9
(c) 12 (d) 15
Q26. The numbers of Zeeman components for 3D2 → 3P1 transition are
(a) 3 (b) 6
(c) 9 (d) 12
Q27. The numbers of Zeeman components for 3D3 → 3P2 transition are
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(a) 6 (b) 9
(c) 12 (d) 15
Q28. In the presence of external weak magnetic field, spectral line split into various
zeeman components called π and σ components. If longitudinal and Transverse
observation defined as view perpendicular and parallel to magnetic field, which of the
following statement is not true?
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(a) In longitudinal observation π-component is absent.
(b) In longitudinal observation both σ components are plane polarized.
(c) In transverse view, π, σ+ & σ – are present.
(d) In transverse view, all π, σ+ & σ – are plane polarized.

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Q29. Atom is placed in a 1T magnetic field and suitably excited. How far apart are the
Zeeman components of the 650 nm spectral line of this element is?
(a) 0.197 nm (b) 1.97 nm
(c) 0.0197 nm (d) 0.00197 nm

2
Q30. The number of hyperfine components for fine spectral line P3/ 2  2 S1/ 2 of

Deuterium atom is

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(a) 1 (b) 2 (c) 3 (d) 4

2
Q31. The spectral term, S1/ 2 level of an atom is single and does not have any fine

structure. The nuclear spin is I  3 / 2 . In a transition from a single hyperfine component

of 2 P1/ 2 , the relative intensity of transition to the various hyperfine components of 2
S1/ 2

is
(a) 3 : 5 (b) 5 : 3 (c) 9 : 5 (d) 5 : 9
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Q32. The number of hyperfine components for fine spectral line 2P3/2 → 2S1/2 of
hydrogen atom is
(a) 1 (b) 2
(c) 3 (d) 4

Q33. For the sodium doublet, D2 & D1, their intensities ratio (D2 : D1) for kT >> ∆ E is
(a) 1 : 2 (b) 2 : 1
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(c) 1 : 1 (d) 3 : 1

Q34. Which of the following is not allowed electric dipole transition?

(a) 1P1 → 1S0 (b) 3P1 → 3P0
(c) 3P2 → 3P1 (d) 3P1 → 1S0

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Q35. Following are observed series in the emission spectrum with their name.
Emission spectrum Series Name
(i) ns → 3p, n > 3 (A) Principal series
(ii) np → 3s, n > 2 (B) Sharp series
(iii) nf → 3d, n > 3 (C) Diffuse series
(iv) nd → 3p, n > 2 (D) Fundamental series
Find the correct match
(a) (i) – (A); (ii) – (B); (iii) – (C); (iv) – (D)

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(b) (i) – (A); (ii) – (B); (iii) – (D); (iv) – (C)
(c) (i) – (B); (ii) – (A); (iii) – (C); (iv) – (D)
(d) (i) – (B); (ii) – (A); (iii) – (D); (iv) – (C)

Q36. Doppler half-intensity width of the sodium D lines at 5893 Ǻ corresponding to a

temperature of 500 k is (atomic weight of Na is 23)
(a) 0.2 Å (b) 0.02 Å
(c) 0.002 Å (d) 0.0002 Å
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0
Q37. Doppler half-intensity width of the sodium D lines at 5893 A corresponding to a
temperature of 500 K is (atomic weight of Na is 23 )
0 0 0 0
(a) 0.2 A (b) 0.02 A (c) 0.002 A (d) 0.0002 A
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Q38. In Hydrogen atom, which of the following transitions are allowed under electric
dipole transition?
(i) 2 P3 / 2  2 s1 / 2 (ii) 2s1/2 → 2p1/2 (iii) 2d3/2 → 1p1/2
(iv) 2d5/2 → 2p3/2 (v) 2f7/2 → 2d3/2
(a) i, ii, iv and v (b) i, ii, iii and iv (c) i and ii (d) i, ii, iv and v

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Q39. Which of the following correctly represent the type of dominant multipole
 E1, E 2, E 3.... M 1, M 2, M 3 for spontaneous photon emission by an excited atomic

electron in each of the following transitions?

(i) 3d 3/ 2  2s1/ 2 (ii) 2 p3/ 2  2 p1/ 2 (iii) 3d3/ 2  2 p1/ 2

(a) M 1, E 2 for (i) & (ii) and M 1 for (iii)

(b) E1, M 2 for (i) & (ii) and E1 for (iii)
(c) M 1, E 2 for (i); E1, M 2 for (ii) and E1 for (iii)

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(d) M 1, E 2 for (i) & (ii) and E1 for (iii)

Q40. J and I is the angular momentum and moment of inertia of a rotating molecules. The
Hamiltonian and type of molecules are listed.
Hamiltonian Type of molecules

J x2 J y2 J2
(i) H    z (A) Symmetric molecules
2 I xx 2 I yy 2 I zz

J x2  J y2 J z2
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(ii) H   (B) Spherical molecules
2 I xx 2 I zz

J x2  J y2  J z2
(iii) H  (C) Asymmetric molecules
2 I xx
Match the correct one
(a) (i) – (A) (ii) – (B) (iii) – (C)
(b) (i) – (C) (ii) – (A) (iii) – (B)
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(c) (i) – (B) (ii) – (C) (iii) – (A)
(d) (i) – (A) (ii) – (C) (iii) – (B)

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Q41. Moment of Inertial Molecule type

(i) Ixx = Iyy Izz = 0 (A) CH3F
(ii) Ixx = Iyy > Izz (B) CH4
(iii) Ixx = Iyy < Izz (C) BCl3
(iv) Ixx = Iyy = Izz (D) OCS
(v) Ixx ≠ Iyy ≠ Izz (E) H2O
Choose the correct match:
(a) (i) – (D); (ii) – (C); (iii) – (A); (iv) – (E) ; (v) – (B)

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(b) (i) – (A); (ii) – (D); (iii) – (B); (iv) – (C) ; (v) – (E)
(c) (i) – (E); (ii) – (A); (iii) – (C); (iv) – (B) ; (v) – (A)
(d) (i) – (D); (ii) – (A); (iii) – (C); (iv) – (B) ; (v) – (E)
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Q42. Following is the statement of rotational constant B, where B  , which
8 2 IC
decide the spacing of Rotational spectrum.
(i) B depends on the axis of the rotation
(ii) B is same for CH4 in all 3 axis of rotation
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Choose the correct option
(a) only (i) is true (b) only (ii) is true
(c) both (i) and (ii) are true (d) Neither (i) nor (ii) is true
Q43. Following is the statement whether molecule is Raman active or not. It must be
noted that a molecules must possess anisotropic polarizability to be Raman active.
(i) CH4 & SF6 does not show pure rotational Raman spectrum
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(ii) CH4 & SF6 shows vibrational Raman spectrum
Choose the correct option:
(a) only (i) is true
(b) only (ii) is true
(c) both (i) and (ii) are true
(d) Neither (i) nor (ii) is true

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Q44. The carbon monoxide  CO  molecule has a bond length of 0.113 nm and the

masses of the 13
C and 16
O atoms are respectively 1.99  1026 kg and 2.66  10 26 kg .
The energy of the photon emitted during rotational transition J  2  J  1 is
(a) 9.5  10 3 eV (b) 9.5  10 2 eV (c) 9.5  10 4 eV (d) 9.5  10 5 eV

Q45. How many normal modes of vibration do the C6 H 6 molecule have?

(a) 36 (b) 30 (c) 33 (d) 34

Q46. Which of the following is IR Active?

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(a) C6H6 (b) CH2 CH2
(c) CH3 CH3 (d) None
Q47. Which of the following is Microwave inactive?
(a) CH3Cl (b) H2O2 (c) N2O (d) CH2CH2
Q48. When CO molecules are dissolved in liquid Carbon tetra chloride, Infrared
radiation of frequency 6.42  1013 Hz is absorbed. Carbon tetrachloride by itself is
transparent at this frequency, so the absorption must be due to the CO . The force
12 16
constant of the bond in the CO molecule is (The masses of C and O atoms are
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1.99  1026 kg and 2.66  10 26 kg )
(a) 5896 N / m (b) 1860 N / m (c) 2980 N / m (d) 3518 N / m
Q49. The microwave transition J = 0 → J = 1 in HCl molecule occurs at 20.68 cm-1. The
wave number of the radiation absorb in J = 14 → J = 15 is
(a) 30.34 cm-1 (b) 150.12 cm-1
(c) 212.10 cm-1 (d) 310.2 cm-1
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Q45. Read the following statement
(i) Rotational spectrum lines of OCS is more closely spaced than CO molecule.
(ii) 16OC16O is microwave inactive while 16OC18O is active
Choose the correct option:
(a) only (i) is true (b) only (ii) is true
(c) both (i) and (ii) are true (d) both (i) and (ii) are false

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Q46. Which of the following statements is not true?

(a) Antisymmetric stretch mode of CO2 is IR active.
(b) Bending mode of CO2 is IR active
(c) Symmetric stretch mode of H2O is IR inactive.
(d) Antisymmetric stretch mode of H2O is IR active.
Q47: The microwave transition J = 0 → J = 1 in HCl molecule occurs at 20.68 cm-1. The
wave number of the radiation absorb in J = 14 → J = 15 is
(a) 30.34 cm-1 (b) 150.12 cm-1

ks
(c) 212.10 cm-1 (d) 310.2 cm-1
Q48. The wavenumber of the incident radiation in a Raman Spectrometer is 20487 cm 1 .


The wave number of first stoke line is B  1.9896 cm 1 
(a) 20475 cm 1 (b) 20499 cm 1 (c) 11.9 cm 1 (d) 7.96 cm 1
Q49: In a diatomic molecule, the internuclear separation of the ground and first excited
electronic state are different as shown in the figure.
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v'
3
2
1
0

Energy v"
2
1
0

Internuclear distance
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If the molecule is initially in the lowest vibrational state of the ground state, then the
absorption will appear as
(a) (b)

energy energy

1 1
v (cm ) v (cm )

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(c) (d)
continnum

energy energy

1 1
v (cm ) v (cm )

Q50: The NMR spectrum of 2-iodo-propane (CH3)2CHI comprises of two lines. The
number of spectral lines in the bunch corresponding to CHI group is:

ks
(a) 1 (b) 3
(c) 6 (d) 7
Q51. Which one of the following electronic transitions in Neon is NOT responsible for
LASER action in a helium-neon laser?
(a) 6s → 5p (b) 5s → 4p
(c) 5s → 3p (d) 4s → 3p
Q52. Considering the coupling between the groups containing hydrogen nuclei. The
NMR spectrum of (CH3)2CHI is obtained. The NMR peak of CHI group consist of X sub
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peaks with intensities ratio (I) as
(a) X=3 and I = [Link]
(b) X= 4 and I = [Link]
(c) X=5 and I = [Link]
(d) X= 6 and I = [Link]
Q53. Consider the CO molecule as a diatomic rigid rotor with a bond length of 1.12Å.
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The reduced mass of the system is obtained from the atomic masses of C and O. The
rotational energies are defined in terms of B (the rotational constant) and J (the rotational
quantum number). If  1 and  2 denote the frequency of the first rotational resonance lines

for the molecules 12C16 O and 13C18O respectively, their ratio  1 and  2 is approximately
(a) 1.5 (b) 1.1 (c) 0.9 (d) 1.01

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54. The NMR spectrum of 2-iodo-propane (CH3)2CHI comprises of two lines. The
number of spectral lines in the bunch corresponding to CHI group is:
(a) 1 (b) 3
(c) 6 (d) 7
Q55. Consider a He  Ne laser  0  0.6328  m  with R1 R2

d  30 cm, n0  1, R1  1 and R2  0.99 . The Passive cavity line

width is (assume   0,  is absorption co-efficient and

ks
ln 1.01  0.01 ) d

(a) 0.8 MHz (b) 0.2 MHz (c) 1.5 MHz (d) 0.1MHz

Q56. Ruby is three level laser in which

  3m sec
concentration of Cr 3 ions in the crystal is E3 0
  4000 A
1.6  1019 Cr 3 ions cm 3 . Considering the average E2 0

E`1   6600 A
pumping frequency of 6.25  1014 Hz and
E`0
zi
spontaneous emission time of the upper level is
3 m sec , the minimum power per unit volume required to maintain population inversion
in this three level laser system is
(a) 1500 Wcm 3 (b) 110 Wcm 3 (c) 1100 Wcm 3 (d) 150 Wcm 3
Q57. In a two beam interference pattern the maximum and minimum intensity values are
found to be 25 I0 and 9 I0 respectively, where I0 is a constant. The intensities of the two
interfering beam are:
fi
(a) 16 I0 and I0 (b) 5 I0 and 3 I0
(c) 17 I0 and 8 I0 (d) 8 I0 and 2 I0
Q58. A three level system of atoms has N1 atoms in level E1, N2 in level E2 and N3 in
level E3 (N2 > N1 > N3 and E1 < E2 < E3). Laser emission is possible between the levels:
(a) E3 → E1 (b) E2 → E1
(c) E3 → E2 (d) E2 → E3

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Q59. When the refractive index μ of the active medium changes by ∆μ in a laser
resonator of length L, the change in the spectral spacing between the longitudinal modes
of the laser is (c is the speed of light in free space)
c c
(a) (b)
2(    ) L 2L
c 
(c) (d) zero
2 L  (    )

ks
Q60. The bond length of H2 is 0.07417 nm. In the pure rotational Raman spectrum of H2
molecules the first anti-stoke’s line will appear at wave number (cm-1)
(a) 363.44 (b) 242.29
(c) 726.88 (d) 121.15

Q61. The internuclear distance in N2 molecule is 0.1098 nm. In the pure rotational
Raman spectrum of N2 the first and second stoke’s line will appear at (in cm-1). Atomic
mass of N = 140 amu.
zi
(a) 3.96, 7.92 (b) 7.92, 15.84
(c) 11.88, 19.8 (d) 11.88, 15.84

Q62. The force constant of the bond in 1H35Cl is 516 Nm-1 which is anharmonic oscillator
with anharmonicity constant xe = 0.0174. In vibrational Raman spectrum, the stoke’s line
will appear at (in cm-1)
fi
(a) 2987.65 (b) 2883.68
(c) 2779.7 (d) 5663.39

Q63. The vibrational constants ωe and ωexe of HCl are 2937.5 cm-1 and 51.6 cm-1.
The first Raman stokes lines will be observed at (in cm-1)
(a) 2834.3 (b) 2885.9
(c) 2989.1 (d) 3040.7

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Q64. The internuclear distance in the nitrogen (14N2) molecule is 0.1094 nm. Raman
spectrum of N2 at NTP is excited by light of wavelength 5,000 Ǻ. The wavelength of the
pure rotational Raman transition (stoke’s line) with J" = 4 as the initial state will appear
at
(a) 5022 Ǻ (b) 5033 Ǻ
(c) 5011 Ǻ (d) 5044 Ǻ
Use the following data to attempt questions 31 to 35. 65 to 69
Data for the molecule 1H35Cl

ks
Internuclear distance = 1.293 Ǻ
Bond Force constant = 516 N/m
Atomic mass of 1H = 1 amu and 35Cl = 35 amu
Where 1amu = 1.673 x 10-27 kg
Q65. The lowest or zero point vibrational energy (E0) and the fundamental vibration
frequency (  0 ) is
(a) 0.186 eV, 8.96 x 1013 Hz
(b) 0.0186 eV, 8.96 x 1012 Hz
zi
(c) 1.86 x 10-3 eV, 8.96 x 1011 Hz
(d) 1.86 x 10-4 eV, 8.96 x 1010 Hz
Q66. The rotational constant B in the ground state is
(a) 11.08 cm-1
(b) 10.28 cm-1
(c) 10.51 cm-1
fi
(d) 10.93 cm-1
Q67. If the rotational constant in ground and higher vibrational levels are same, then the
wave number of the lines P(1), P(2), in P-Branch is (in cm-1)
(a) 2945.6, 2925.1 (b) 2976.4, 2966.14
(c) 2966.14, 2945.6 (d) 2925.1, 2904.46

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Q68. If the rotational constant is same in all vibrational state, then the wave number of
the lines R(0), R(2) of R-branch is (in cm-1)
(a) 2986.7, 3007.26 (b) 3007.26, 3027.82
(c) 3007.26, 3038.1 (d) 3007.26, 3048.38

Q69. The value of ωe and ωexe for H2 is 4395cm and 118 cm-1 while for D2 is 3118 and
64 cm-1 The zero point vibrational frequency (in cm-1) of H2 and D2 is
(a) 2197.5, 3054 (b) 2168, 1543

ks
(c) 4277, 3054 (d) 2079.5, 1495

Q70. The fundamental vibration mode of 1H 35Cl observed at 2886cm-1. The wave
number of the corresponding mode of 2H 35Cl is
(a) 4025.9 cm-1 (b) 3051.2 cm-1
(c) 2951 cm-1 (d) 2069 cm-1

Use the following data to attempt questions 71 to 72.

zi
The 3883.4Ǻ fundamental band of CN molecule is represented by a formula
 cm 1   25798  3.850m  0.068m 2 where m = 0, ±1, ±2, ±3 …..

Q71. The value of rotational constant B’ and B” is

(a) 3.918 cm-1 & 3.782 cm-1 (b) 1.28 cm-1 & 1.21 cm-1
(c) 1.959 & 1.891 cm-1 (d) 1.28 cm-1 & 1.35 cm-1
fi
Q72. The location of band head is (in cm-1)
(a) 25744 (b) 25639
(c) 25832 (d) 25548

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Use the following information to solve questions from 73 to 74:

Following is the vibrational-rotational spectrum of CO molecule under very low
resolution and at T = 300K.

R - Branch
P - Branch

ks
v1 v 0 v2 v ( cm 1 ) 
The band is centred at 2143 cm-1 while the average line separation near the centre is
3.83 cm-1
Q73. The wave number v1 (cm-1) at which P-branch intensity maximum lie,
(a) 2173.15 (b) 2127.2
(c) 2131.21 (d) 2116.7
Q74. The wave number  2 (cm 1 ) at which R-branch Intensity maximum lie, is
zi
(a) 2158.78 (b) 2183.12
(c) 2173.15 (d) 2191.25
Q75. The exciting line in an experiment is 5460 Ǻ and stokes lines at 5520 Ǻ. The
wavelength of the anti-stoke line is
(a) 5134 Ǻ (b) 5201 Ǻ
(c) 5291 Ǻ (d) 5401 Ǻ
fi
Q76. A substance shows a Raman line at 4567 Ǻ, when exciting line 4358 Ǻ is used.
The position of stokes an anti-stoke line for the same substance when the exciting lien
4047 Ǻ used, is
(a) 4226 Ǻ, 2812 Ǻ (b) 4226 Ǻ, 3882 Ǻ
(c) 5187 Ǻ, 3102 Ǻ (d) 5187 Ǻ, 3882 Ǻ

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Q77. Which of the following statement is not correct?

(a) All the molecules H2O, H2O2, NH3, N2O shows show a pure rotational microwave
absorption spectrum:
(b) All the molecules CH2Cl2, CH3CH3, SF6, N2O shows rotational Raman Spectrum.
(c) The molecules CH3CH3, CH4, CHCI3 all are IR active
(d) The normal modes of vibration for molecules: C6H6, C6H6CH3, and HCC-CCH are
30, 42 and 13 respectively.
Q78. The pure rotational levels of a molecule in the far infrared region follows the

ks
formula εJ = B J (J +1), where εJ is the energy of the rotational level (in cm-1) with
quantum number J and B is the rotational constant. The separation between lowest
stoke’s and antistokes line in rotational spectrum is
(a) 4 B (b) 8 B
(c) 10 B (d) 12 B
Q79. The separation between P(3) and R(1) lines
(a) 102.8 cm-1 (b) 5932.28 cm-1
(c) 5973.4 cm-1 (d) 5952.84 cm-1
zi
fi

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Objective Questions (Atomic and Molecular Physics)-Solutions

Ans1: (b)
Solution: The condition of mechanical stability of the electron (mass m, charge e) moving
mv 2 e 2
with velocity v in an orbit with radius a is  2
a a
nh
The quantum condition is mva  , n = 1, 2, 3 ……..
2
2e 2 n 2h2

ks
These gives v  , a
nh 4 2 me 2
The number of revolutions of the electron in the orbit per second is

v 4 2 me4  2 2 me 2  2c  2c 
f   3 3
 3  3  R  3 
2 a nh  ch  n n 
For n = 2 state, the frequency of revolution is

h c 1.097 10 cm  3 10 cm sec 

5 1 10 1

f    8.2 1014 sec1

4 4
Hence the revolution of the electron in the life time of 10-8 sec.
zi
= (8.2 x 1014) x 10-8 = 8.2 x 106 sec-1
Ans2: (d)
Solution: In case of positronium atom, the two particle have the same mass me, so the
mM ' me2 m
reduce mass is m    e
m  M 2me 2
m e
'
 Bohr radius r  e' rn  2rn
n
e
fi
m
 m'  E E
while En'    12  12
 me  m 2n

E1
For n = 1, r1'  2r1  2a0 & E1' 
2
In case of muonic atom, mμ = 207 me and Mp = 1836 me

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 207me 1836me 
 m'   186me
207me  1836me 
 me  1 P
 r1'   '
 a0  r1  a0
 186me  186

 86me 
and E1'    E1  186 E1
 me 
Ans3: (a)

ks
Solution: The Rydberg constant for the hydrogen and ionized helium are
R R
RH  and RHe 
m m
1 e 1 e
MH M He
where R∞ is the Rydberg constant for an infinitely heavy nucleus. Since MHe ≈ 4 MH
me
1
R 4M H 4 M H  me
 H  
RHe 1  me 4  M H  me 
MH
zi
E1 me4
while R    2 3  R∞ = 1.097 x 107 m-1
ch 8 0 ch
Ans4: (b)
M m'
Solution: Rydberg constant for atom is RM  R  R
me  M me
where M is the nucleus mass and R∞ is Rydberg constant for a heavily nucleus.
For hydrogen atom
fi
me M m  1836me
m'   e  me
me  M me  836me
 R1  R

For Positronium atom M  me

me R R
R2  R    1  R1  2 R2
me  me 2 2

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Ans5: (a)
Solution: The wavelength of the photon released when electron jump from initial (higher)

1  1 1 
state ni to final (lower) state nf is  R 2  2 
 n 
 f ni 
where R is the Rydberg constant

1  1 1 
for Bracket series: nf = 4 ;   R 2  2  where ni  5,6,7........
  4 ni 

ks
1 1 1 
for Pfund series: nf = 5;   R 2  2  where ni  6,7,8........
 5 ni 

Series limit occurs when ni = ∞

 Series limit of Bracket and Pfund is
1 1  1  1  B 16
 R  0 &  R   0  
B  16  p  25   p 25
Ans6: (c)
 1 1 
Solution: E  E f  Ei  E1  2  2 
zi
 n f ni 
 
1 1 
ni  1, n f  3 and E1  13.6 eV , so E  13.6  2  2  eV  12.1 eV
3 1 
Ans7: (d)
Solution: Here m  207 me , M p  1836 me

So the reduce mass is

fi
m M p  207 me 1836 me   m  186 me
m  
m  M p 207 me  1836 me

Now, the ionization energy is

 m 
E1    E1  186 E1  186   13.6 eV   E1  2.53 keV
 m

The ionization energy is therefore 2.53 keV

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Ans8: (b) Solution: The interaction energy of a dipole moment  s in a magnetic field

 eh 
 is int   s      sz   where  sz is z-component of  s   sz   
 4m 
eh
  int   
4m
The difference in energy of the electrons having spins parallel and antiparallel to the field
is ms  1/ 2

ks
eh  eh  E1
  1  2   
4 m  4 m  E


eh

1.6  1019    6.63  1034 
 1  1.856 10 23 J
E2
31
2 m 2  3.14  9.1 10
4
ms  1/ 2
 1.16  10 eV
Ans9: (d)
Solution: The fine structure of atomic spectral lines arises because of interaction between
spin and orbital angular momentum of electrons. The magnetic field produce by orbital
and spin motion of electron couple together and causes the splitting in the spectral lines.
zi
Ans.10: (a)
12400 12400 3 p3 / 2
Solution: E1   eV  , E2   eV 
 
0  0 2 B B
1  A  2  A 3p
   
0 0 3 p1 / 2
Where 1  5896 A and  2  5890 A 1 2
3s
12400 12400 3s1 / 2
 E1   2.103 eV ; E2   2.1053 eV
5896 5890
fi
 The separation between 3P3/ 2 and 3P1/ 2 is E  2.13  10 3 eV

But the separation between 3P3 / 2 and 3P1/ 2 is also equal to 2 B B , where  B is Bohr


magnetron  B  9.27  10 24 J / T 
E 2.13  1013  1.6  1019 J
E  2 B B  B    18.5 T
2B 2  9.27  10 24 J / T

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Ans11: (d)
Solution: The angular quantum number for 3Po state is J = 0

The magnetic moment is   g B J J  1  0

Ans12: (c)
Solution:
The phenomena of Lamb shift is caused by the interaction between the electron and an
electromagnetic radiation field. A quantized electromagnetic radiation field in its lowest

ks
energy state is not one with zero electromagnetic fields, but there exist zero-point
oscillations similar to harmonic oscillator. This mean even in vacuum there are
fluctuations in this zero-point energy which act on electron. This causes electron to
execute rapid oscillatory motion, which leads to shift in energy level.
Lamb observed experimentally that 2 2S1/2 and 2 2P1/2 are not degenerate but 2 2S1/2 is
0.035 cm-1 higher than that of 2 2P1/2.
Ans13: (d)
Solution: The fine structure of atomic spectral lines arises because of interaction between
zi
spin and orbital angular momentum of electrons. The magnetic field produce by orbital
and spin motion of electron, couple together and causes the splitting in the spectral lines.
Ans14: (c)
Ans15: (a)
Ans16: (c)
Solution: The energy order of spectral term is decided by Hund’s rule for equivalent
electrons:
fi
i. The spectral terms with largest multiplicity lie lowest.
ii. Of the terms with given multiplicity, the largest L lie lowest.
iii. For less than half filled sub-shell, the level with lowest J lies lowest.
iv. For more than half-filled sub-shell, the level with highest J lies lowest.
v. For half-filled sub-shell, S-term is the lowest.

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Ans17: (a)
Solution: The interaction between intrinsic magnetic moments of the proton and the
electron leads to hyperfine splitting. The interaction Hamiltonian is
H = - μp.B
Where B is the magnetic field produced by the magnetic moment of the electron and μP is
the intrinsic magnetic moment of the proton.
In the ground state, the electron charge density is spherically symmetric so that B has the
same direction as the electron intrinsic magnetic moment μe. Since the electron has

ks
negative charge, therefore, μe is antiparallel to the electron spin Se.
For the lowest energy state of H, (μp . μe) >0 and so (Sp . Se) < 0
Thus the singlet state F = 0 is the ground state, on the other hand, the triplet F = 1 is an
excited state.
Ans18: (b)
Solution: Since the separation of doublet state proportional to the fourth power of atomic
number as given by spin orbit coupling.

T Li Z Li 4 32
zi
2
Thus,    81   T  Li2  81 0.365  29.6 cm-1
T H  X H 2 14

Ans19: (d)
Solution: The electronic configuration in excited state is 1s2 2s2 2p5 3s1
Pauli’s allows S = 0 & S = 1 for L =1
For S = 0, L =1 → J =1
For S = 1, L =1 → J = 2, 1, 0
fi
The possible states in term of (L, S, J) are (1, 1, 2) ; (1, 1, 1) : (1, 1, 0) & (1, 0, 1)
Ans20: (b) Solution: The optical electrons are in 3d orbit
M L  2  1 0  1  2

5 5
In this configuration: L  0 and S  J 
2 2
2 s 1
Thus spectral term is LJ  6S5/ 2

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Ans21: (b)
eB
Solution: The separation of the Zeeman component is v 
4 m
c d 2 eB 2
since v  , dv   c 2   v 
  c 4 mc
2

 
1.6  10 C   0.3T   4.5  10 m
19 7
0
 2.83  10 12 m  0.028A
 4   9.1  10 kg 3  10 m / s 
31 8

ks
Ans22: (d)
Solution: Both the term 1 F3 and 1D2 are singlet term (S = 0) the Lande g-factor is 1. The
separation between consecutive Zeeman level is the same for both terms.
This transition will give only 3 components.
Ans23: (a)
Solution: The terms 2P3/2 and 2S1/2 corresponding to J = 3/2 & J = 1/2 will break into
2J+1 Zeeman levels, which is 4 and 2 respectively.
For 2P3/2 Mj = - 3/2 -1/2 +1/2 +3/2
For 2S1/2 Mj = -1/2 +1/2
zi
The selection rule is
∆MJ = 0, ± 1 (MJ = 0 → MJ = 0 If ∆J = 0)
∆MJ = 0 gives π component
∆MJ = ±1 gives σ component
Total π component = 2
Total Zeeman component = 2 x 3 = 6
fi
Ans24: (b)
Solution: For 2D3/2 : Mj = - 3/2 -1/2 +1/2 +3/2
For 2P1/2 : Mj = -1/2 +1/2
Total π component = 2
Total Zeeman component = 2 x 3 = 6

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Ans25: (c)
Solution: For 2D5/2 : Mj = -5/2 - 3/2 -1/2 +1/2 +3/2 +5/2
For 2P3/2 : Mj = -3/2 -1/2 +1/2 +3/2
Total π component = 4
Total Zeeman component = 4 x 3 = 12
Ans26: (c)
Solution: For 2D3/2 : Mj = -2 -1 0 +1 +2
For 2P1/2 : Mj = -1 0 +1

ks
Total π component = 3 (since ∆J ≠ 0, thus MJ = 0 → MJ = 0 is allowed)
Total Zeeman component = 3 x 3 = 9
Ans27: (d)
Solution: For 3D3 : MJ = - 3 -2 -1 0 +1 +2 +3
For 3P2 : MJ = -2 -1 0 +1 +2
Total π component = 5 (MJ = 0 → MJ = 0 since since ∆J ≠ 0)
Total Zeeman component = 5 x 3 = 15
Ans28: (b)
zi
eB
Ans29: (c) Solution: The separation of the Zeeman components is v 
4m
d 2 v
since v = c/λ and dv  c   
2 c
2
eB 2 1.6  10  1   6.5  10 
-19 -7

v    1.97  10-11m    0.0197 nm

4 mc  4   9.1 10  3  10 
-31 8
fi
Ans30: (d)
Solution: For Deuterium: I 1 F  5/2
2P3 / 2
while J  3 / 2 for 2 P3 / 2 and J  1/ 2 for 2 S1 / 2 3/ 2
1/ 2

Selection rule is F  0,  1 0 
 0 2S 1 / 2
3/ 2

1/ 2

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Ans31: (b)
Solution: For 2S1/2, J = 1/2 & I = 3/2  F = I + J and I – J = 2 and 1
According to the sum rule, with a hfs multiplet the ratio of the sum of the intensities of all
transitions from states with quantum number F and F' are in the ratio of their statistical
weights (2F + 1) : (2F' + 1). Here the intensities of transition starting from a single level
and ending on the hyperfine levels with F = I + J and I – J are in the ratio
 1
2 I    1
2F  1 2  I  J   1  2 I 1 5

ks
     Ratio = 5 : 3
2 F ' 1 2  I  J   1  1 I 3
2 I    1
 2 

Ans32: (c) F 2
2
1 P3 / 2
Solution: For H1 : I=½
F 1

2 F 1
S1 / 2

Selection rule is ∆F = 0, ± 1 0 
 0 F 0
zi
Ans33: (b)
Solution: When kT >> ∆E, the intensity ratio D2/D1 is calculated by the degeneracy’s of
2
P3/2 & 2P1/2.
3
2 1
D2 2 J 2  1 2
  2
D1 2 J 1  1 1
2 1
2
fi
Ans34: (d)
Solution: The selection rules for single electric dipole transition are
∆l = ± 1, ∆ j = 0, ± 1
The selection rules for multiple electric-dipole transition are
∆S = 0, ∆ L = 0, ± 1, ∆ J = 0, ± 1 0 
 0
(d) forbidden transition as it violates ∆S = 0

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Ans35: (d)
 2 RT 5893  1010 2  8.31 500
Ans36: (b) Solution:   1.67 0  1.67   0.02Å
c M 3  108 23
Ans37: (b)

0 2 RT 5893  1010 2  8.31  1023  500

Solution:   1.67  1.67   0.02Å
c M 3  108 23  10 23
Ans38: (d)

ks
Solution: For electric transition selection rule must be satisfied
(i) l  1 (ii)  j  0,  1 (iii)  s  0 (iv) Parity must change
Thus option (d) is the only correct option.
Ans39: (d)
Solution: (i) 3d 3 / 2  2 s1/ 2 : L  1, 2 P   ve
 transition is M 1 or E 2
(ii) 2 p3 / 2  2 p1/ 2 : L  1, 2 P   ve
 transition is M 1 or E 2
zi
(iii) 3d 3 / 2  2 p1/ 2 : L  1, 2 P  ve
 transition is E1
Ans40: (b)
Solution: According to classical physics, the kinetic energy of rotation of a body of

1 2
J q2
moment of inertia Iqq about an axis q is T   I qq  q  q 2 I
2 q qq
fi
Where ωq is the angular frequency about the axis and Jqq = Iqq ωq.
There is no contribution from the potential energy, so the Hamiltonian is

J x2 J y2 J2
H    z
2 I xx 2 I yy 2 I zz

For spherical molecules: Ixx = Iyy = Jzz

For symmetrical molecules: Ixx = Iyy ≠ Izz
For Asymmetrical molecules: Ixx ≠ Iyy ≠ Izz
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Ans41: (d)
Solution: OCS: Linear molecule: Ixx = Iyy & Izz = 0
CH3F: Symmetric top (Prolate): Ixx = Iyy > Izz
BCl3: Symmetric top (oblate): Ixx = Iyy < Izz
CH4: Spherical top: Ixx = Iyy = Izz
H2O: Asymmetric: Ixx ≠ Iyy ≠ Izz
Ans42: (c)
Solution:

ks
B is inversely proportional to moment of inertia, while, moment of inertia may or may
not be same in all direction. So B depends on the axis of rotation.
CH4 is spherical top molecule, for CH4, Ixx = Iyy = Izz. So B is same in all 3 directions.
Ans43: (c)
Solution:
CH4 & SF6 are spherical top molecules. Their Polarizability is isotropic i.e. does not
change with rotation. Thus both are rotationally Raman inactive as well as microwave
inactive.
zi
While, in vibration mode, the polarizability changes when spherical molecule contract
and expand in diameter, such polarizability is called breathing polarizability. Thus, CH4
& SF6 are vibrational Raman active.
Ans44: (c)
Solution: The reduce mass of the CO molecule is
mc mo 1.99  2.66
   10 26 kg    1.14  1026 kg
fi
mc  mo 1.99  2.66
and its moment of inertia is
2
  
I   r 2  1.14  1026 kg 1.13  1010 m  I  1.46  1046 kg  m 2

The lowest rotational level corresponds to J  1 , and for this level in CO

2

E J 1 
J  J  1  2  2
 

1.054  1034 J  s 
 7.61  10 23 J  4.76  10 4 eV
46 2
2I I 1.46  10 kg  m

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The energy corresponds to J  2 is

2

EJ  2   
 34
6 2 3 2 3  1.054  10 J  s   7.61  10 23 J  1.43  10 3 eV
2I I 1.46  10 46 kg  m 2

 E  E J  2  E J 1  1.43  103  4.76  10 4  9.5  10 4 eV  95 meV

Ans. 45: (b)

Solution: Total degree of freedom is 3 N  3  12  36
Translational degree of freedom is T  3

ks
Rotational degree of freedom is R  3
 Vibrational degree of freedom V  3 N  T  R  36  3  3  30
Ans46: (d)
Ans47: (d)
Ans48 :( b)
Solution: The reduce mass of CO is
mc mo 1.99  2.66
   10 26 kg  1.14  10 26 kg
mc  mo 1.99  2.66
zi
1 k
whereas, vo   k  4 2vo2 
2 
2

k  4 2  6.42  1013 Hz   1.14  10 26

kg  1860 N / m

Ans49: (d)
Solution: The wave number for J → J + 1 transition is v  2 B  J  1
fi
For J = 0 → J = 1, we get v  2 B
Given v  20.68cm 1  B  10.34cm 1
Now wave number for J = 14 → J = 15 will be
v  2 B14  1  30B  30  10.34
v  310.2cm 1

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Ans45: (a)
Solution: (i) The moment of inertia of OCS is more (because r is large) than CO. thus its
rotational constant B is smaller, hence rotational lines are more closely spaced.
(ii) The molecules differ in isotope have same bond length. CO2 has net zero dipole
moment in all isotope.
Ans46: (c)
Solution: For CO2: Antisymmetric stretch and bending mode is IR active while
symmetric stretch mode is IR inactive

ks
For H2O: All the modes are IR active
Ans47: (d)
Solution: The wave number for J → J + 1 transition is v  2 B  J  1

For J = 0 → J = 1, we get v  2 B
Given v  20.68cm 1  B  10.34cm 1
Now wave number for J = 14 → J = 15 will be
v  2 B14  1  30B  30  10.34
zi
v  310.2cm 1
Ans48: (a)
Solution: The wave number of Raman line is
vR  vo  B  4 J  6

where +ve and –ve sign is for anti-stoke and stoke line.
For first stoke line  J  2  J  0
fi
vR  vo  6 B  20487  6  1.9896  20475.1 cm 1

Ans49: (b)
Ans50: (d)
Ans51: (c)
Ans52: (d)

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 1 B1 I 2  2
Ans53: (b)     1.1
 2 B 2 I 1 1

Ans54: (d)

Ans55: (a)
2n0 d
Solution: The cavity life time is tc  where x  1  R1 Rz e 2 d
  1 
c ln  
  1  x 

ks
Thus   1  1  0.99 e  o  1  0.99  0.01 and 1  x  0.99

 1   1 
ln    ln   ln 1.01  0.01
1 x  0.99 
2  1  30  10 2 m
Thus tc   0.2  106 sec
3  108

m / s  0.01

The passive cavity line width is

1 1 1
v p   6
 Hz  v p  0.8 MHz
2 tc 2  0.2  10 1.26  10 6
zi
Ans56: (c)
Solution: The minimum pumping power per unit volume required to maintain the
population inversion is

Pmin 
N hv p 1.6  1019 cm 3
 
  
6.6  10 34 J  s  6.25  1014 Hz 
 1100 Wcm 3
3
2  2 3  10 sec
fi
A
ns57: (a)
= 25I0, = 9I0.
Ans58: (b)
Ans59: (a)

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Ans60: (a)
Solution: Reduce mass of H2 molecule is
MH MH 1 1
  MH   1.673  10  27  0.84  0 27 kg
MH  MH 2 2


Moment of Inertia    r 2  0.84 10 27  0.07417 10 9 
2
= 0.462 x 10-47 kgm2
Thus, the rotational constant B (cm-1) is
h 27.9907  1047 27.9907 1047
B    60.573cm 1

ks
8 2 c I 0.462  1047
The wave number of stoke’s and anti-stoke’s line
v R  v exc    4 J  6 
The + sign is for anti-stoke’s and – sign for stoke’s line
The consecutive anti-stoke’s line appears at higher wave number side from vexc at
  4 J  6 
Therefore   4 J  6  , where J = 0,1,2,3…….
The first anti-stoke’s line appear at (when J = 0)
zi
∆ε = 6B = 6 x 60.573 = 363.44 cm-1
Ans61: (c)
14 1.673 10 27 14 1.673 10 27
Solution: The reduce mass (μ) =
14  141.673 1027
=11.711 x 10-27 kg
Moment of inertia (I) = μr2 = 11.711 x 10-27 x (0.1098 x 10-9)2 =1.412 x 10-46 kgm2
fi
6.625 10 34
Rotational constant (B) = h/8π2Ic ; B  2  46 10
 1.98cm 1
8 1.412 10  3 10
The stoke’s lines will at ∆ε = B (4J + 6) cm-1 on lower wave number side from exciting
wave number
∆ε = B(4J + 6) where J = 0, 1, 2, 3,……
first stoke’s line : ∆εs = 6B = 11.88 cm-1
second stoke’s line : ∆εs = 10B = 19.8 cm-1

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Ans62: (b)
1.673 10 27  35 1.673 10 27
Solution: Reduce mass of 1H35Cl (μ) =
1  351.673 10 27
= 1.627 x 10-27 kg
The relation between wave number (ωe) and force constant (K) is

1 K
e 
2c 

ks
1 516
Thus,  e   27
 2987.65 cm 1
2  3  1010 1.627  10


The Raman lines appear at v R  v ex   fundamental cm 1 
where minus sign represents the stoke’s lines and appear at lower wave number side at
∆εfundamental = ωe (1 – 2xe) = 2987.65  0.9652 = 2883.68 cm-1
Ans63: (a)
The vibrational Raman displacement is v   fundamental = ωe (1 – 2xe)= 2834.3

Ans64: (c)
zi
1 14
Solution: The reduce mass of N2 is   M N  1.673 10 27 = 11.711 x 10-27 kg
2 2
Moment of inertia I = μr2 = 11.711 x 10-27 x (0.1094 x 10-9)2 = 1.4 x 10-46 kgm2
h 6.625  1034
The rotational constant B  2
; B  2 46 10
 1.998 cm 1
8 c 8 1.4  10  3  10
The Raman shift
∆ε = B (4J + 6) where J = 0, 1, 2, 3, ……
fi
For J = 4; ∆ε = B (16 + 6) = 22B = 22 x 1.998 cm-1 = 43.95 cm-1
The wavenumber of stoke’s line will be
1
v s  vex      = 20,000 cm-1 – 43.95 cm-1 = 19956.05 cm-1
exc
o
1
 stokes   5011 A
vS

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Ans65: (a)
 1
Solution: The vibrational energy is Ev   v   hosc ;  v  0,1, 2,3
 2

1 K
where  osc 
2 
K is force constant, its value is given K = 516 N/m
M H M Cl
Reduce mass;  
M H  M Cl

ks
1.67  10 27  35  1.673  10 27
 = 1.627 x 10-27 kg
1  35  1.673  10  27
ωosc = 8.96 x 1013 Hz
Thus the zero point energy is
Ev=0 = E0 = ½ h ωosc = 2.969 x 10-20 J
E0 = 0.186 eV
The fundamental vibrational frequency (v = 0 → v = 1)
 1 1
zi
Ev 1  Ev 0  1  hosc   hosc
 2 2
E  hosc
E
Fundamental frequency =   osc
h
 0   osc  8.96  1013 Hz
Ans66: (b)
fi
h
The rotational constant B = 2
8 Ic

cm 1 
10
I   r 2  1.627  1027  1.293  10   2.72  1047 kgm 2
6.625  1034 Js
B  2 47 2 10 1
 10.28cm 1
8  2.72  10 kgm  3  10 cms

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Ans67: (c)
Solution: In the fine structure of infra-red Band, total energy is
2
 1  1
 BJ  J  1   v   osc  xe  v    osc
 2  2
For the main absorption, ∆v = ±1, (v' = 1 ← v'' = 0)
The wave number for this transition is
   0  B' J '  J '1  B" J "  J "1

ks
For P-Branch: J  J ' J "  1
  P   0  B ' B"J " B ' B"J "2
Since B' = B'' = B
  P   0  2 BJ "
0
where  0   2986.7cm 1
c
and B = 10.28 cm-1
For P(1), J'' = 1   P  2966.14 cm 1
zi
For P(2) , J'' = 2   P  2945.58cm 1
Ans68: (d)
Solution: The wave number for this transition is
   0  B' J '  J '1  B" J "  J "1
For R- Branch: J  J ' J "  1
  R   0  2 B ' 3B ' B"J " B ' B"J "2
fi
since B' = B'' = B
  R   0  2 B  2 BJ "

For R(1) ; J'' = 0   R  3007.26cm 1

For R(2) , J'' = 2   R  3048.38cm 1

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2
 1  1
Ans69: (b) Solution: For anharmonic oscillator  v   e  v     e xe  v  
 2  2
Zero point energy corresponds to v = 0.
1 1
 0   e   e xe
2 4
1 1
For H2:  0   4395  118  2168cm 1
2 4
1 1
 0   3118   64  1543cm 1

ks
For D2:
2 4
Ans70: (d)
Solution: The vibrational energy of a harmonic oscillator is

 1 1 k
E v   v  h  osc where  osc  Hz 
 2 2 
The Fundamental vibration frequency is
E1  E0 1 k
0   osc   in Hz 
h 2 
zi
0 1 k
The corresponding wave number is   
c 2c 

Let 1 &  2 is wave number for

1
H 35Cl and 2
H 35Cl respectively.

2 1 1 35  2  35  35 37 37
       0.7168
1 2 1  35  2  35 36 70 72
fi
2  0.7168  2886 cm 1  2068.7 cm1
Ans71: (c) Solution: The general equation for the rotational lines of a band is
   0   B ' B " m   B ' B " m 2

Compare it with the given equation for the fundamental (V”= 0 → V’ = 1) band is we get
B' + B" = 3.85 cm-1 ; B' – B" = 0.068 cm-1
on solving this equation we get B' = 1.959 cm-1 ; B" = 1.891 cm-1

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Ans72: (a)
Solution:
The value of m at which the vertex of Fortrat Parabola (band-head) lies is obtained by
d
0
dm
B' B"
 mv  
2 B' B"
Thus, band head is

ks
2 2
 B ' B "  B ' B "   B ' B "
 head  0   B ' B "   B ' B " 2
0 
2  B ' B " 4  B ' B " 4  B ' B "

since  0  25798 cm 1
2

 head  25798 
 3.85   25744 cm 1
4  0.068
Ans73: (d)
Solution: The maximum population of levels gives maximum intensity of the transition.
zi
kT 1
The value of J at which this occurs is J  
2hcB 2
For P-Branch: ∆J = -1
  P   0  2 BJ

 kT 1
Now, 1   0  2 B  
 2hcB 2 
fi
Given, 0  2143cm -1 and 2 B  3.83cm 1  B  1.915cm 1

Thus
 1.38  1023  300 1
1  2143  3.83     2143  26.32  2116.7cm 1
 6.63 10  3  10  3.83 2 
34 10
 

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Ans74: (c)
Solution: For R-branch: ∆J = + 1
  R   0  2 B  2 BJ   0  2 B( J  1)

kT 1
The maximum intensity will occur at J "  
2 Bhc 2

 kT 1
2  0  2 B   
 2 Bhc 2 
 

ks
 1.38 10 23  300 1
 2143  3.83   
 3.83  6.63 10  3 10
34 10
2 

 2143  30.1496  2173.15cm 1
Ans75: (d)
1
Soltuion: v0  8
 18315.02cm 1
5460  10 cm
1
vR  8
 18115.94cm 1
5520  10 cm
Raman shift is v  v o  v R = 199.08 cm-1
zi
v does not depend upon the incident frequency and is same for anti-stoke also
v  vas  vo  vas  v  vo  vas  18514.1 cm 1
1 o
as   5401A
vas

Ans76: (b)
Solution: vo  22946 cm 1 , vR  21896 cm 1 ; Raman shift: v  v o  v R = 1050 cm-1
fi
v does not depend upon the incident frequency
1
v0'  8
 24710cm1
4047  10 cm
Thus, the wave number of stokes & anti-stokes lines are
= v'o  v = (24710 ± 1050) cm-1 = 23660 cm-1 amd 25760 cm-1

or λstoke = 4226 Ǻ and λanti-stoke = 3882 Ǻ

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Ans77: (b)
SF6 is Rotational Raman Inactive molecule
Ans78: (d)
Solution: The rotational energy levels of linear molecule is
εJ = B J (J +1)
Selection rule ∆J = 0, ±2
For ∆J = +2 : ∆ε = B (4J + 6) cm-1 (J = 0, 1, 2, ….)
Thus if the molecule gains rotational energy with collision from photon, we get S-branch

ks
lines at lower wave number side of the exciting line called stokes line, while if molecule
looses energy to the photon the S branch line appear on the high wave number side called
antistoke line. The wave number of the stokes and anti-stoke lines are
v R  v exc  
6B 6B
-1
4B 4B 4B 4B
v R  vexc  B 4 J  6  cm

Stoke' s line v Anti - stoke' s line

exc
zi
The separation between lowest Stoke’s and Anti-stoke’s line is = 12B
Ans79: (d)
Solution:  P   0  2 BJ "

For P(3), J''=3   P ( 3 )  2925.02cm 1

And  R   0  2 B  2 BJ "
For R(1), J'' =1   R (1)  3027.82
fi
Separation between P(3) and R(1)
   P ( 3)   R (1)  5952.84cm 1

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