Candidate's Nurnber

qStHGE OF CHEIWICAT SC]ENCES

INSTITUTE OF CI.IEMISTRY CEYTON

GRADUATESHIP EXAMINATION IN CIIEMISTR.Y 2019

C 31012 _ SPECIAL TOPICS IN PITYSICAL CHEMISTRY I

DURATION: TWO (02) HOURSp/zs 10 mins reading time

No. of Questions: 04 No. of Pages: 14

1. Answer AII Questions.

2. The marks allocated to each question or parts of a question are indicated on the right hand
side.
3. The question paper contains two parts (A & B) and questions 1 -3 in part A and 4 in part B.
The answers to all questions should be submitted as per instructions by the chief examiner.
Part A and part B will be collected separately.
4. If these instructions are not followed correctly, 10 % of total marks will be deducted as pef,
college policy. Each question carries equal amount of marks.
5. Mobile phones are not permitted.
6. The use of'a non-programmable electronic calculator is permitted. However, the memory
on your calculator must be erased before you enter the examination hall.

(FOR EXAMINER',S USE ONLY)

 Part A

I. Vibrational and rotational motions of a diatomic molecule can be approximated as a

harmonic oscillator and rigid rotor respectively.

Mention under which conditions each approximation is valid to describe vibrational and
rotational motions of molecules. Justify your answer. (10 marks)

o Harmonic oscillator

o Rigid rotor

II The energy levels of a harmonic oscillator are givcn by En = o (i): @ * ))

(a) Define al1the terms. What are the possible values tbr n? (10 marks)

(b) Deduce an equation for the zero point energy of a harmonic oscillator. (5 marks)

(c) Derive an expression for the fundamental vibrational frequency of a harmonic oscillator
in terms of k, and pr using the above equation for energy levels. (5 marks)
The grourid state wave function of a harmonic osciliator is given by tlto|) - (1)''^ ,-ax212

where o: (*)'''
(d) Show that i/6(x) is normalized. (10 marks)

(e) Show that ( x2 > : [i*r/r}) x' ,!oG) d.x = h/z,[ktt (10 marks)

(0 < )cz >L/z is the square root of the mean of the squares of the displacement and also
known as the root mean square displacement (RMSD) of the oscillator. Show that
RMSD of bond distance of a diatomic molecule
h
is4rvU where v is its fundamental
vibrational frequency. (10 marks)
 (g) The fundamental vibrational frequency of HCl is 2890 cm-t. Detemine the RMSD of
bond distance and oompare that with the experimental bond length ofHCl (i.e. 127 pm).

(10 marks)

m. The energy levels of a rigid rotor are glven by \ =fi I U + I)

(a) Define the terms. What are the possible values of -r. (5 marks)

@) Find an expression for the frequency of transition between the lh and.I+lfr energy
levels in terms of the rotational constant 8, where B = ( 10 marks)
#.

.- v.
',t

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 (,:) The rlicro\,,,a\ e spectrurrr cif IIC1 eonsists of series cf equail1, spacecl trines. separated by
6.21xl011 Hz. What is the value of rotationai constant irlr HCl'/ (10 marks)

Question 2

Name four systems which can be solved exactly using quantum mechanics. (10 marks)
*

il. Write down the Schrodinger equation for a hydrogen atom using polar coordinates. Abbreviate
all the notations in your equation. Kinetic energy operator for a rotor in quantum mechanics is

-*ztt ,' {You

\ don't have to expand the Laplacian operator} (15 marks)

5
III. The general solution to the three-dimensional hydrogen atom is of the form

lbn t(r, 0, Q) = R(r)n,Y{" (e, Q)

where R(r)n is the radial wavefunction and Y{"(0 ,Q) are the spherical harmonics.

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*i,,,-a
R n, = tffif#)' (h)' L?,!i | (#)
where the form of the first few tunctions 4ll (#) with x =
# are given below.

l; t.r1 ' -- 1

tl"(xi -= l.r, - +

rl1 r:i .. l
l-ltr) -, 3.rr.i"lli-r*1li
L,t-r) '- -(r:r+18
(a) What is the significance of the Bohr radius a6? (5 marks)

(b) Describe the quantum numbers n,l, & m arrd state the possible values that each
quantum number can take. (i5 marks)

(c) Identiff the quantum numbers that describe the 3s atomic orbital of a hydrogen atom.
(05 marks)

(d) Find the numerical value for the orbital angular momentum of an electron in this orbital
(i.e. 3s orbital). (05 marks)

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(e) Show that the 3s radial wavefunction Rrrs of the hydrogen atom is

2 rLt3/2
n \A) Q7 - tao * 2o2)e-o/3
whereo=rfas
(15 marks)
(0 Which of the following probability density plots represents the radial part of the 3s
wavefunction? (indicate A, B or C) Give the reason for your choice. (10 marks)

I{3 15
nlm*

(g) What are approximate r value for each node/s in 3s orbital? (you don't have to solve
any equation) (05 marks)

(h) What is the extra information you need to determine the full 3s wavefunction? (5
marks)

(i) Write a mathematical expression (integral with limits) to find the probability of an
electron inside the first radialnode of a 3s orbital and simplify it. (You don't have to
evaluate the final integral, but must show the integrals with correct limits.) (10 marks)

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Question 3

Tetra chloromethane CCl+ belongs to the Ta point group. The following vibrational modes
have been observed in its IR and Raman spectra.

fR wavenumber / cm-l Raman wavenumber / cm-l

305 2t8
768 324
458
762

CCl+ has Cz, Cz and S+ axes of symmetry and a o4 plane of symmetry. Draw suitable
diagrams and show these symmetry elements. (10 marks)

(i) Complete the following table to obtain the reducible representation of the total degrees
of freedom (I37y) forthis molecule. (15 marks)

Td E 8C:
Unshifted
atoms
Contribution
per atom
l:rv

Note contribution per atom for C, and Sn sl,mmetry operations are given by

cn = 7* 2 cos (ryJ *us,, = -1 + z cos (ry)

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II. By applying reduction fonnuia (given beiow) deter:nine the nurnber of times each
ttrec
in'educible represenration occurs in the surn.

N(k) =
;>,g" xk(c) x(c)
N(k) -Number of times kft irreducible representation occurs in the sum
h - Ordq of the group
g" - Number of symmetry operations in class
Xkk) - Character of class c in the ineducible representation k
XG) - Character of the class I in the reducible representation
(15 marks)

k Calculations N(k)

Character table for the Ta point group

T E EC'r 3Cr tSa 6o,t

l
Ar I I 1

A: 1 _i -t
'l
E I 0 0
Tl 0 -1 I -1 (R*-. R...R-'r
Tr ,1 0 I

m. Determine the total reducible representation (137y) of this molecule. (10 marks)

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r IV. Show that the reducible representation for the vibrational modes is Ir;1 - (Ar + E + 2Tz)
(after subtracting translational and rotational contributions). (10 marks)

V. Determine the reducible representation for stretching modes using intemal coordinates for
stretching modes. (i.e bonds) (30 marks)

First, obtain the reducible representation of the lstutch i.e Number of upshifted coordinates
(Complete the table below).

Td E BC:
lsiv

\-. By applyng the reduction formula determine the number of times each irreducible
representation occurs in the sum. Show all the calculations. (Complete the table below)

k Calculations N(k)

What is reducible representation for the stretching modes?

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VI. Determine reducible representations for bending (deformation) modes (in CCl+ all
vibrational modes are either stretching or bending). (05 marks)

VII. Determine the representation for the IR active modes and Raman active urodes. (05 marks)

VIII. Representation of the vibrational modes are shown in the diagram below.
(a) Assign the symmetry labels for each modes
(b) Assign degeneracy of each mode (singly, doubly, triply)
(c) Label IR active and IR inactive modes
(10 marks)

t2
 Candidate's Number

eSil.E€iE 0F CHERltt€At rclENeEs

INSTITUTE OF CHEMISTRY CEYLON

GRADUATESHIP EXAMINATION IN CHEMISTRY 2018

Part B

(FOR EXAMINER',S USE ONLY)

Question No. Part Marks Marks

4.

Question 4

L Calculate the nurnber of normal modes of viblation for the deuterium oxide (DzO) molecule.
110 marks)

il. Sketch the normal modes of vibration for deuterium oxide (Du O) molecule. Name and label the
vibrations. (15 marks)

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III. Which are the parallel and perpendicular vibrations among the above vibrations? Mark the : '
variation of dipole moment during each vibration. (05 marks)

ry. The fundamental and first overtonebands of the IR spectrum of CO appear at2143 cm-1 and
4260 cm-t respectively. Calculate the equilibrium vibrational frequency ( ur) and the
anharmonicity constant (1). Use any of the following expressions.

LE.*.ofh=(1 -ZX)v"
AEz-o/lL = (1 - 3y)2v"
LE',*o/h-(1 -4"tr)3v"
(25 marks)

t4
VIIL Using another sketch show how the spectral lines are arranged in this region. (10 marks)

D(. Briefly explain the intensities of the observed spectral lines and why they converge to a
continuum. (10 marks)

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