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(b) Pauli's Exclusion principle (quantum mechanical
[This Question paper contains 8 !l.4'."t:tWiLj ( IV))
approach) · Your Roll No .
Sr. No. of Question Paper : 1113 I
( c) Configuration Interaction
Unique Paper Code 2172013503
(d) Variation Theorem (5,5,5)
Name of the Paper Quantum Chemistry and
Covalent Bonding
Name of the Course B.Sc. (Honours) Chemistry
Maximum Marks : 90
Instructions
l. Write your Roll No. on the top immediately on receipt
of this question paper.
2. Attempt only six questions out of eight.
3. Use of scientific calculators and Logarithmic tables is
allowed.
4. Attempt all parts of a question together.
(2000} P.T.O.
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(b) Show that operators corresponding to x and Px
Physical Constants . do not commute. Give the physical significance of
34
Planck 's constant 6.626 x 1 o- J s your result.
Velocity of Light 3 X 108 ms"
(c) What do you understand by Hermitian operators?
Avogadro's Number 6.022 x 1023 mol"
Prove that all the eigen values of Hermitian
Mass of Electron 9.1 X 10-31 kg (5,5,5)
operators are real numbers.
1
Boltzmann Constant 1.38 X 10-23 J K·
7. (a) Write the LCAO-MO trial wave function of H;,
using Molecular Orbital approach. Derive the
1. (a) A particle of mass m, in a one-dimensional box of expressions for molecular orbital wave functions
length a can be represented by the function, corresponding to the bonding and anti-bonding
energy levels of H;.
tf,,(x) = sin n:x (n=l,2,3 ... ). Normalize the given
(b) Plot the radial probability distribution functions for
function \\f(x) and find whether it is an eigen an electron in hydrogen atom where n = 1 and
function of (i) Px (ii) P!· n = 2. Explain the plots briefly.
( c) Explain the significance of orthonormality principle
(b) Write four properties of a function to make it
giving relevant mathematical expressions.
acceptable as a solution of Schrodinger equation. (5,5,5)
Determine whether the following functions are
acceptable or not acceptable as state functions 8. Write short notes on any three:
over the interval indicated, giving apprnpriate
(a) Postulates of Quantum Mechanics
reasons.
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5. (a) Show that the wave functions describing the Is'
atomic orbital and the 2s atomic orbital for the Function Interval
hydrogen atom are orthogonal. Given that
(-1, +1)
(1- x2rl
exp(-x) (0, 00)
312
.~(2.)
t/J2s = 4v2rr a 0
{2 - (r/a0)} exp(.2ao
.: !:. )
where a0 is Bohr's radius and
J0
00
r71 exp(-ar) dr = n!/aCn+i).
(c) Evaluate the commutator [Lx, r;J where Lx and r;,
are the angular momentum operators along the x
and y-direction respectively. (5,5,5)
(b) Set up the Hamiltonian operator for a particle
oscillating about a mean position (a simple
harmonic oscillator). Explain the significance of 2. (a) Are the following functions eigenfunctions of the
zero-point energy of a simple harmonic oscillator.
d2
operator -? If so, give the eigen value.
dx2
(c) Why the quantum number 'n' cannot be assigned
a zero value while solving for the particle in a 1-
D box? Give the units of
D box.
\j/ 2 for a particle in a I-
(5,5,5)
(i) f(x) ~ exp[ <J
(ii) cos 2x
6. (a) A particle of mass m exists in a one-dimensional
(b) Consider a particle of mass 'm' in a cubic box of
box of length L. Using the trial wave function
edge length 'L'. What is the degeneracy of the
\j/trial = Nx(L - x) evaluate the energy associated
with the lowest energy level and comment on level that has energy three times the lowest energy
whether this trial wave function is an acceptable ? Write the mathematical expressions for the
function according to the variation theorem. degenerate wavefunctions.
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( c) If A and B are two atoms bonding along the z- (c) Write the electronic configuration of H2, H/ and
axis predict, giving reasons, which of the following hypothetical H2- species using molecular orbital
theory. Explain why He/ exist whereas He2 does
atomic orbitals can combine:
not. (5,5,5)
4. (a) A diatomic molecule can be treated as a simple
.. )
( 11
A
<fJ1s and <fJ2s
B quantum mechanical oscillator. How is the simple
Schrodinger Wave Equation (SWE) modified for
(5,5,5) this system? Show that
(i) expr-Bx") is a solution to this SWE and
3. (a) Write the expression for the Hamiltonian operator
for the helium atom explaining briefly all the terms (ii) E = ..!.. ~, here k is the force constant
involved. Simplify this expression using the Bom
47r ✓µ
and µ is the reduced mass)
Oppenheimer approximation. Write the expression
for the corresponding Schrodinger's equation.
(b) What is the degeneracy of each of the following
energy levels of H atom?
(b) Evaluate the expectation value of the radius, (r),
at which the electron in the ground state of
Hydrogen atom (Z=l) is found. Given the wave
function for this state is
(c) Explain and calculate zero point energy (ZPE)
,I,
'1'1,0,0
1 ( z )3/2
= vii ao
zr) where a is the Bohr
exp ( - ao of an electron in a one dimensional box of
0
infinite height and I A length. State the Bohr's
radius and f 00
rnexp(-ar)dr = a<:! >. Correspondence principle. (5,5,5)
1
0
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