Roll Number:

Thapar Institute of Engineering and Technology, Patiala

School of Chemistry and Biochemistry
END SEMESTER EXAMINATION
M. Sc. (First Year): Semester-I (2017/18) Course Code: PCY104
Course Name: Quantum Chemistry
December 7, 2017 Thursday, 14.00 — 17.00 Hrs
Time: 3 Hours, M. Marks: 100 Name Of Faculty: Dr. Dibyendu Mallick

Note: Attempt all questions in sequential order and be brief and to-the-point.
Assume missing data, if any, suitably

Q1. Answer the following questions. (1 X 10)

(a) State true (T) or False with valid reason: The Schroedinger equation of H2 molecule can be
solved exactly.
(b) Write the conditions for two wavefunctions, ip,(x) and tirj(x) to be orthonormal.
(c) Calculate the number of degenerate states for Hydrogen atom for n = 4.
(d) Write the electronic Hamiltonian for He atom.
(e) What is the physical significance of the following commutator relationship? [11, E21 = 0
(f) State true (T) or False: When a beam of Ag atom is passed through a non-uniform magnetic
field it splits into three beams.
(g) Calculate the magnitude of the orbital angular momentum for H-atom for I =2.
(h) How many microstates are possible for d2 configuration?
(i) Arrange the following states (term symbols) for p2 configuration in the increasing order of
energy: 11), 3P and 15
(j) Plot the probability density profile for a particle confined in an one dimensional box of
length L for n = 2.

Q2.
(a) For a particle of mass m confined in a cubic box of edge L
i) Draw schematic energy level diagram for all possible states within the energies 0 to
17h2 /8mL2. How many states are there within the energies 0 to 17h2/8mL2?
ii) What is the degeneracy of the state having energy 14h 2 /8mL2?
iii) How many energy levels lie in the range 0 to 17h2/8mL2?, ( 3+1+1)

(b) Draw and compare the energy level spacing at n = 1, 2 and 3 for a particle in a box of lengths
(i) L and (ii) 2L using schematic energy level diagrams. (5)

Q3.
(a) The work function for the platinum metal is 5 eV. Which radiation of wavelength will exhibit
photoelectric effect; 200 nm or 900 nm? Estimate the velocity of the electron ejected from
the surface. [given that 1eV = 1.602 x 10-19 j; Mass of an electron (me). 9.1 x 10 -31 kg and h =
6.626 x 10-34 Js] (5)

(b) Calculate the de Broglie wavelength of an electron which has a kinetic energy of 13.6 eV.
.31 (5)
[1eV = 1.602 x 10.19 J; Mass of an electron (me). 9.1 x 10 kg]

1.0
Q4.
(a) Prove that eigenvalues of Hermitian operators are real. (5)
d2 2
(b) A certain system is described by the Hamiltonian operator R = dx2+
-- X
-x2
(i) Show that IP = Axezis a eigenfunction of R; determine the eigenvalue.
(ii) Determine A so that the function is normalized.

[Hint: Use the integral jr c° 2 e —x2 dx = 4

] (3+2)

Q5.
(a) A crude treatment of the it electrons in a conjugated system regards these electrons as
moving in the particle-in-a-box potential, where the box length is somewhat more than the
length of the conjugated chain. The Pauli Exclusion Principle allows no more than two
electrons to occupy each energy level. For butadiene (CH2=CH-CH=CH2), take the box length
as 7.0 A and use this model to estimate the wavelength of light absorbed when a 7 electron
is excited from the highest occupied level to lowest-vacant level. (5)

(b) To a good approximation, the microwave spectrum of H-35C1 consists of a series of equally
spaced lines, separated by 6.26 x 1011 Hz. Calculate the bond length of H-35C1. [1 a.m.0 =
1.66 x 10-27 Kg, h = 6.626 x 10-34 Js] (5)

Q6.
(a) The solution of the radial part of the Hydrogen atom is given by
3
( 2 V2- (n - / - 1)! — p /21 p
RnI(P) = - 7.1.ao ) 2n((n + 003 e
2r
where p =
nao
ds
Lsp(p) = — Lp(p)
dps
dP
and Lp (p) = eP —(pPe-P)
dpP
From above expressions derive the expression for the radial function for is orbital (R10 (r)) of
Hydrogen atom. (4)

(b) Sketch the following plots for Hydrogen atom with proper labeling of the axes.
(I) R20 (r) vs. r
(ii) R21 (r) vs. r
(iii) Radial distribution plot for R20 (r)
The respective radial functions are given below. Here Z = 1.
Z 2 (1 Zr _Zr/tau
B20 = 2 „
zao 2ao c4,

1 Z (Zr) _ czr/2au
R21 =
\/ 2a 0 a() (2+2+2)
Q7.
(a) Show that [0, Lz ] = 0 . Given that [Li, Ly] = ihriz [Ly, Li] = IhLX ,[Li,Lx ] = ihLy. (5)
(b) Using generalized uncertainty principle, i.e., dil211B2 — [< [A, 9] >]2 , show that Ax Apx
h/2; where A and B are any arbitrary quantum mechanical operators. (5)

Q8.
(a) Derive the first order correction in energy using perturbation theory for the ground state of
any arbitrary system. (5)

(b) Use the potential given below as a perturbation term to the Hamiltonian of the particle in a
one-dimensional box and calculate the first order correction to the ground state energy of
the system.
OC x < ()
V (x) () < <
a
.V >u
(5)

Q9.
(a) State and prove the variation theorem. (5)

(b) Derive the litickel MO theory for ethylene/ethene. Draw simple schematics of the bonding
and anti-bonding energy level diagrams (5)

Q10.
(a) Calculate the Bond Orders (B.O.) of 02+, 02 and 02- using Molecular Orbital (MO) theory.
Which one has the highest bond distance among the above three molecules. (5)

(b) Draw the MO diagram for H2O molecule. (5)

All the Best

Note: The evaluated answer sheets will be shown on 22nd December, 2017 between
10.00 AM to 12.00 Noon at FC-202, TAN Building