RAMNIRANJAN JHUNJHUNWALA COLLEGE, GHATKOPAR (W), MUMBAI 400 086

AUTONOMOUS
Subject: Physics (Course: RJSPGPHY204)
Atomic and Molecular Physics
CLASS: M.Sc. PART-I SEM-I| ATkT
DAY:
DATE:
Gaturday
2 a42023
TIME: :00m tb l:30p
Maximum Marks: 60

1.. Attempt any two.

(A) Consider analkali atom and transition from doublet (Pn,Ps2) ’Si2. How many
line willbe observed. Discuss splitting of these levels and its effect on spectrum when
this atom is placed in magnetic field. [8 Marks]
(B)(i) Hyperfine interaction is a result of interaction between Nuclear spin magnetic moment
that depends on nuclear spin I and electron total magnetic moment resulting out of orbital
and spin magnetic moment which depends on total angular momentum j. V#ES = a l.j
Cesium has a nuclear spin of 7/2. How many lines will the hyperfine spectrum of the D
line of the Cesium atom will consists of ?

(ii) Write notes on exchange force. [4+3 Marks]

(C) (i) Write down quantum numbers for the states described in spectroscopic notation as
S32,D, and P3. (ii) Determine if any of these states are impossible, and if so explain
why. [4+3 Marks]

2. Attenmpt any two.

element.
(A) (i) Explain sudden discontinuity in filling up electronic shells of following
3V=(1&Ar) 3d'4s and 24Cr =(1RAr) 3d°4s' [4 Marks]

F = 3ao v/s Bohr model

(i) Discuss prediction of Hartree theory that for large Z elements
prediction , « n? [4 Marks]

diagram for this

(B) Consider 2p3s configuration of°C atom. Draw schematic energy level
notation.
configuration in LS coupling scheme, Label each level with its spectroscopic
Explain your working in detail. [7Marks]

P-T.0
(C) lonisation energy of Ar (Z= 18) is I5.8 ev Calculate effective quantum number and
quantum defect,.
Refer to the figure below showing radial probability density and Z(). What is Zeff ln s
shell. Estimate the total energy of electron in the 3rd shell.

18

Argon

05 1.0 .5 20 3.0 35 A.0

rla,

What is spectral notation for ground state of Argon. Explain your working. [7 Marks]
3. Attempt any two.

1
(A) Consider wave functions b, = e ao and
(4na)î
1
sin 8 e.Check iftransition from state 2to state l is
(6a2) 8T \2a¢/
allowed in dipole approximation with necessary calculation. (7Marks) )
(B) For interaction of electromagnetic radiation with one electron atom, we start with
Schrodinger equation ih o = (H, + H),
Ze2 and H'= ihe
where H,=-y2 m
-A.V
2m 4TEoT

Starting with wave function y(T,t) =}k Ckt)()elik/, where (F) are
unperturbed eigenfunctions of HÍ with eigenvalues Eg . Determine time dependent
coefficient c) using time dependent perturbation theory. ldentify each term in cÁ)
with correct interpretation.
[7Marks]

P.T.0
02
(C) () Write notes on X-rays. Explain origin of continuous and characteristic spectrum. What
are Auger transitions?

(i) Write a short note on Line shape and line width. [4 +4 Marks]

4. Attempt any two.

at
(A) (i) The first rotational Iine C°O is obseryed at 3.84235 cm ' and that of "CO
3.67337 cm - Calculate the atomic weight of C, assuming the mass
(molecular
[3 Marks]
weight) of °O to be 15.9949.
215 cm and the
(ii) The equilibrium vibration frequency of the iodine molecule is
band y=1’ y =2
anharmonicity constant x, = 0.003. What is the intensity of the hot
temperature is 300 K?
relative to that of the fundamental v = 0 ’y =1, if the
[4 Marks]
[4 Marks]
(B) (i) Discuss molecular orbital theory for H2" ion.
of "NN is observed at
(ii) The first Stoke's lines in the rotational Raman spectrum
(c) Will there be
11.5416 cm.(a) What is its B value? (b) Calculate its bond length
"NN show a rotational
an intensity alteration in the spectrum of"NN? (d) Would
[3 Marks]
spectrum?

molecule are 1.593 cm and

(C) (i) Rotational and centrifugal distortion constants of HCI
constant of
5.3x10 cm respectively. Estimate the vibrational frequency and force
the molecule.
[3 Marks]

an instrument
(ii) Electron spin resonance is observed for atomic hydrogen with
2.0026,
operating at 9.5 GHz. If the g value for the electron in the hydrogen atom is
what is the magnetic field applied? Bohr magnetron 4a =9.274x10-2 JT.
[3 Marks]
homopolar diatomic molecules
(iii) Why is it that pure rotational spectra can not be observed for
but Raman rotational spectra can be? [2 Marks]
 RAMNIRANJANJHUNJHUNWALA COLLEGE,GHATKOPAR (W), MUMBAI 400 086
AUTONOMOUS
Subject: Physics (Course: RJSPGPHY204)
Atomic and Molecular Physics
CLASS: M.Sc. PART-I SEM-II
DAY: Friday TIME: 2:00 pm - 4:30 pm
DATE: 21/04/2023 Maximum Marks: 60

1. Attempt any two

(A)() Construct a diagram showing spliting of levels in magnetic field with transitions
allowed by selection rules between the singlet states 2p3s ('P ) and 2p('D; ) of the °C
atom. (ii) Verify that the normal Zeeman pattern of three spectral lines willbe produced
in these transitions. (ii) Evaluate the difierences in wavelength of these three spectral
lines when the atom is in external field of 0.1 tesla. [3 +3 +2 Marks

(B)(i) Write down quantum numbers for the states described in spectroscopic notation as
'S32, 'D, and P,. (ii) Determine if any of these states are impossible, and if so explain
why. [4 +3 Marks]

(C)() Hyperfine interaction is a result of interaction between Nuclear spin magnetic moment
that depends on nuclear spin and electron total magnetic moment resulting out of orbital
andspin magnetic moment which depends on total angular momentum j. VArs = aij
Cesium has a nuclear spin of 7/2. How many lines will the hyperfine spectrum of the D
line of the Cesium atom willconsists of ?
(ii) Write notes on exchange force. [4 +3 Marks]

2. Attempt any two.

(A) Jonisation energy of Ar(2 = 18) is 15.8 eV. Calculate effective quantum number and
quantum defect.
Refer to the figure below showing radial probability density and Z(r). What is Zer in 3
shell. Estimate the total energy of electron in the 3 shell.

Pro
 20|
18

16

Argon

25 30 35 4.0

What is spectral notation for ground state of Argon. Explain your working. [8
Marks]
(B) Consider 2p3s configuration of °C atom. Draw schematic energy level
diagram for this
configuration in LS coupling scheme, Label each level with its spectroscopic notation.
Explain your working in detail. (7Marks]

(C) Write notes on Central field approximation. [7 Marks]

3.Attempt any two.

(A) For interaction of electromagnetic radiation with one electron atom, we start with

Schrodinger equation ih=

at (Ho +H)y,
Ze2
where H, =-2.
27n
and H'=eAV
4TTE0T m

Starting with wave function Uit) = k C&(t)y (FeiEt/h where are

unperturbed eigenfunctions of Ho with eigenvalues Ex . Determine time dependent
coefficient cÁ) using time dependent perturbation theory. Identify each term in cá)
with correct interpretation.
(8Marks]
(B) For vector potential A(r,t) = Ag(w)£ cos(k.r- wt +S) , calculate expression for
(i) electric and (ii) magnetic field. [2+5 Marks]

PTO
(C) () Discuss doppler broadening and pressure broadening and its cffect on line
width and
line shape. [3 Marks|
(11) Write notes on X-rays. Explain origin of continuous and characteristic spectrum.
What
are Auger transitions? [4 Marks]

4. Atempt any two.

(A)()Why is it that pure rotational spectra can not be observed for homopolar diatomic molecules
but Raman rotational spectra can be? [2 Marks]
(11) The first three rotational Raman lines of alinear triatomic molecule are at 4.86, 8.14 and
11.36 cm 'from the exciting Raman line. Estimatethe rotational constant Band the
moment of inertia of the molecule. [3 Marks]
(ii) The equilibrium vibration frequency for an oscillator is observed at 2990 cm". The
ratio of the frequencies corresponding to the first and the fundamental spectral lines is
1.96. Considering the oscillator to be anharmonic, calculate the anharmonicity
constant. [3 Marks]

(B) () Discuss principle of NMR (Nuclear Magnetic Resonance) with necessary theory.

(4 Marks]

(ii) Discuss the effect of anharmonicity on the vibrational spectra of diatomic molecules.
[3 Marks]

(C) Discuss H, molecule as per Heitler-London theory. [7Marks]

3 je
 S.P. Mandali's
RAMNARAIN RUIA AUTONOMOUS COLLEGE
MATUNGA, MUMBAI 400019.
SEMESTER END EXAMINATION

SEMESTER -IV CLASS - M.Sc. SUBJECT: PHYSICS

TITLE - ATOMIC AND PAPER CODE: RPSPHY402
MOLECULAR PHYSICS
DAY- THuRSDAY DATE - 16/0B} 202 TIME: $:o0 Am To 10130 Am
DURATION - 2.5 HOURS MAX MARKS: 60

N.B: -
1. All questions are compulsory
2. All questions have internal choice
3. Figures to the right indicate full marks
Q1 (A) Attempt any One: (8
a) Consider one- electron atoms. To obtain the fine structure of such a system, write
down the Schrodinger equation including the relevant corrections in the
Hamiltonian. ldentify these terms. Obtain the energy shift due to the relativistic
kinetic energy term.
Youmay use <>nm and < >nm=
r
aj n (i+1)
b) Consider two- electron atoms. What are singlet and triplet states? Explain why the
ground state of helium exists in the para state whereas the excited state has both
para and ortho states.
i a) Write down the complete Schrodinger equation for one electron atom in a
constant magnetic field, including spin-orbit interaction but neglecting the reduced
mass effect, the relativistic kinetic energy term etc. Identify the iamagnetic and
paramagnetic terms. Which one is a larger term? Neglect the smaller term and
consider the case Bext >> Bint. Which quantum numbers are to be used to
calculate energy shifts and why? Obtain the energy shift, neglecting the spin-orbit
term.

b) What is isotopic shift? Obtain an expression for the energy shift 8E due to the
isotopic Volume effect and show that it increases when Z increases and n
decreases.
Q1 (B) Attempt any One: (7)
a) If thehyperfine interaction in anatom is given by H =a S, S, where S, and S
denote the electron and proton spins respectively. What is the splitting between
the S, and Sostates in terms of h2?
1
 b) Show that Hydrogen atom in the ground state does not show Stark effect.
a) What is Lamb shift? What is the reason for using radio fregquency technique to
measure it?

b) Consider the eight, n = 2 states, 12,L, j, m, >, Find the energy of each state, under
weak field Zeeman splitting.
Q2 (A) Attempt any One: (8)
i
lonisation energy of Ar (Z =18) is 15.8eV. Calculate effective quantum number and
quantum defect.
Refer tothe figure below showingradial probability densityand Z(). What is Zo in 3
shell. Estimate the total energy of electron in the 3 shell.

P) Argon

0.5 30 3.5 4.0

rla

What is spectral notation for ground state of Argon. Explain your working.
ii
Discuss Hartree theory, its results and predicitons.
Q2 (B) Attempt any One: (7)
i Consider 2p3s configuration of °C atom. Draw schematic energy level diagram for this
configuration in LS couplingscheme, Label each level with its spectroscopic notation.
Explain your working in detail.
Write notes on Central field approximation.
Q3 (A) Attempt any One: (8)
1
Consider wave functions , = Te ao and
(4naj)+
1
de -T/2a0 cos . Check if transition from state 2 tostate 1 is

allowed in dipole approximation with necessary calculation.

2
 For

m Aw

Jo

Interpret the terms. Calculate an expression for transition rate for spontaneous
emission in dipole approximation.
Q3 (B) Attempt any One: (7)
For vector potential A(r, t) = A(w)êcos(k.r- wt +o).calculate electric and
magnetic field.
Discuss Line shapes and line width consideringdifferent factors that affect it.
Q4 (A) Attempt any One: (8)
i a) What is LCAO approximation? List the conditions to be satisfied by the
contributing atomic orbitals to generate an effective MO.
b) Explain the conditions for a mode of vibration to be Raman active, taking
example of CO, molecule.
a) Explain the principle of ES R. Why microwave source and techniques have to be
applied for its observation?
b) What is isotopic substitution? VWhat effect it has on the rotational spectra of
molecules? What is its use?
Q4 (B) Attempt any One: (7)
a) The microwave spectrum of CN radical shows a series of lines spaced by a nearly
constant amount of 3,798 cm". What is its bond length?
[Given: h = 6.626 x10-34Js, u= 1.0730x 10-26kgl
b) Explain why in H2 molecule the separation between adjacent rotational lines is 4B.
whereas for 0, it is 8B.
a) Obtain the condition that a mode of vibration IR active. Also state the selection
rules.
b) The fundamental and first overtone transitions of C0 are centered at 2143.3 cm
and 4260.0cm'. Calculate the equilibrium oscillation frequency, the
anharmonicity constant and force constant ofthe molecule. [Given: = 1.1385 x
10-26kg.

3
 Hindi Vidya Prachar Samiti's
RAMNIRANJAN JHUNJHUNWALA COLLEGE, GHATKOPAR (W), MUMBAI - 400 086
AUTONOMOUS
ATKT EXAMINATION (SEE)-DECEMBER 2022
CLASS: MSc SEM-II Course : RJSPGPHY204
DAY: Friday am to 1.3060pm
Atomic 8.Molatular PhTIMINGS: 11.00MARKS:
DATE: 09/ 12/2022
1. Attempt any two.
(A) Show that n =2 state of H-atom splits into three in presence of external electric
field. What are energies, wave functions and degeneracies of these states? [8 Marks]
(B)(1) Calculate Zeeman splitting for 'P, and D, levels and effect of this splitting on its
spectrum. (3Marks]
(ii) What happens to atom inmagnetic field? What is the difference between normal
and anomalous Zeeman effect? What is Paschen-Back effect? [4 Marks]

(C) ()Calculate the number of permittedtransitions from ?rPn’'Si2. Explain how you
arrive at your answer. [4 Marks]

(ii) Write notes on exclusion principle for two particle system. (How do we write
wavefunction for such a system?] [3Marks]

2. Attempt any two

(A) Ionisation energy of ssCs is 3.9 eV. Explain this in terms of () Quantum Defect and
(ii) screening of nuclear charge. [7 Marks]

(B) () What is LS and JJ coupling? When do we use them? [3 Marks]

(ii) Calculate the number of spectral lines allowed in the spectrum for 3'D ’3P
transition in sodium. [4 Marks]

(C) Choose the correct option. [Show details of how you arTive at the answer in both the

following questions.J (4 Marks each]

i) The term i jad) arising from 2s'3a' electronic configuration in j-j coupling
scheme are

(a) 2 and )32 (b) 4 and (;

and
(c) 6)1g and 32 (d)

.T.o
 (ii) The allowed states for He (2p) configuration are
(a) 'So, 'Si, 'P Po2. D, and 'Di23 (b)'So, 'Po,12, and 'D,
(c) 'P, and Po12 (d)'So and 'P
3. Attempt any two.
(A) () For oscillator strength given by fo=m0ba|o2, show that Ek fka = 1.
3h

[S Marks]
(ii) Choose the correct option. (2 Marks]
Two states of an atom have definite parities. An electric dipole transition between
these states is
(a) allowed if both the states have even parity
(b) allowed if both the states have odd parity
(c) allowed if the two states have opposite parities
(d) not allowed unless a static electric field is applied

(B) () Explain natural line width using « Draw appropriate graph and
(u-ana/)
explain meaning of each term w.r.t. graph. [4 Marks]

(ii) An atom emits a photon of wavelength = 600 nm by transition from an excited

state of life time 8x10 s. If Av represents the minimum uncertainty in the
frequency of the photon, then calculate the order of magnitude of the fractional
width 4v
of the spectral line. (3 Marks]

(C) By appropriate calculation find whether y211 ’ Vo0 and a10 Vontransitions in
H-atom are allowed? [8 Marks]
4. Attempt any two.
(A)(i) Calculate the force constant of the bond in COmolecule if the spacing between
the vibrational energy levels in is 8.44x10eV. Given that the reduced mass of CO
is 1.14x10-2° kg, h=6.626x10- Jsand 1 eV = l.6x10-J. [4 Marks]
(i0) What is the importance of Raman effect in Rotational spectra of diatomic
molecule?
[4 Marks]

PT.O
02
(B) Discuss rotational Raman spectra for a diatomic molecule with necessary theory.
(7Marks]
(C)() Discuss principle of ESR(Electron spin resonance) with necessary theory.
[(4 Marks]
(1) The excitation wavelength of laser Raman effect experiment is 546 nm. If the
the
Stoke's line is observed at 552 nm, then calculate the wave number (in cm ) of
anti-Stoke's line. (3 Marks]
 S.P. Mandali's
RAMNARAIN RUIA AUTONOMOUS COLLEGE
MATUNGA, MUMBAI 400 019.
INTERNAL CLASS TEST

SEMESTER - IV CLASS- M.Sc. SUBJECT: PHYSICS

TITLE-ATOMIC AND MOLECULAR PAPER CODE: RPSPHY402
PHYSICS
DAY - TUESDAY DATE - 17/01/2023 TIME: 09:00 A.M. to 09:30 A.M.
DURATION 30 MINUTES MAX MARKS: 20

N.B: -
1. All questious are compulsory
2. All qucstions have internal choice
3. Figurcs to the right indicate full marks

CANDIDATE NO.: SUPERVISORIS SIGNATURE:

Q1. Multiple Choice Questions (1 Mark Each): (5)

1 To measure the lamb shift in Hydrogen, Lamb and Rutherford used a method to simulate direct
transition between S/2 and "Pi2. levels. This was done toreduce mainly the Doppler
broadening. For tlhis thcy used
A. Optical Frequencies B Infrared Frequencies
C. Ultraviolct Frcqucucics D. Radio Frcqucncics
2 The slift in the euergy of oue electron atoms due to the relativistic energy tern HË' spi1 orbit
interaction term H; and the Darwin term H,' depcnd on the valuc of thc orbital quantum number
l, the total cnergy corcction due to the addit.ion of all thesc terms depends on:
A. B. ?
C. indepcndcnt of l D. 13

3 The spin - orbit interaction energy for one electron atom,in the electron rest frame is given
by AE = 9s Its valuc in nuclcus rost frame is

1
A. AE = g S B. B. AE 2
PB S. B.
C. AE = 2 gs D.

4. The allowed states for He(2p) configuration are

A. 's, 'S,, 'P, Pul2 'D, and "Di23 B. 'So, Po2, and 'D,
C. P,and "Po2 D. "So and 'P,
The spin-orbit intcraction in an aton is given by H = aL.S wherc L and S denote the orbital
 and spin angular momenta, respectively, of tbe electron. The splitt ing between the level P% 2
and "Pi,2 is
A. ah? B. ah2
3ah? D. ;ah?
Q2. Answer the Following (1 Mark Each) (5)
1. What is hyperfine splitting and isotopic shift?
2. Write down the complete Schrodinger equation for one electron atoms in a constant magnetic field
incuding only the spin - orbit interaction. Which of these terms represent paramagnetic and
diamagnetic terms?
3 What is the degeneracy of n p n' system where l#0and l#1.
4 State Lande Interval Rule.

5 Electronic configuration of GS of Cr : 1s' 2s 2p" 3s 3p" 4s' 3d, Explain this in the light of
Hund's Rule.

Q3 Attempt any two (5 Marks Each) (10)

1. Consider a one electron atom placed in anexternal electric field E in the Z direction. Obtain the
second order correction to the ground state energy which is proportional to ¬.
2 Slhow that the shifts in the frequency for D3/2 and P/2 transitious in the prcscuce of awcak
magnetic ficld is Av = 4m m, - m ).
3. Discuss Spectral notation for GS of 16S.

4. How docs lvalue dccide bchaviour of clectron ncar small r.