Department of Chemistry

Gauhati University CH104

Quantum Chemistry - CH104
Time: 2 12 hr 42 Marks
M.Sc, Sem I, 2020-2021

1. State the physical significance of each of the three summated terms in the kinetic energy operator
of the H-atom in polar coordinates, 3

−~2 1
 
2 1 1 2
Ĥ = ∂r (r ∂r ) + 2 ∂θ (sin θ∂θ ) + 2 2 ∂φ
2µ r2 r sin θ r sin θ

2. State the physical interpretation of the following term. 1

(a) Commutation relationship

3. Find the eigenvectors of the matrix, A:  

3 2
.
4 5
3

4. Find an expression for the energy of a vibrating diatomic molecule assuming that the force of
attraction between the diatomic bond obeys Hooke’s law. 4

5. The wavefunction for an excited electron in Ag atom is given by,

53/2 2z 2 − (x2 + y 2 )
ψ= √ p (6 − ρ)ρ2 e−ρ/2 , ρ = 94r/ao
192 5 (4π) r2

(a) How many nodes are present? 1

(b) Identify the location of the radial node or nodes. 1
(c) Sketch and explain the radial part as a function of r. 2
(d) Predict what type(s) of atomic orbital(s) can it represent. 1

6. Express the Hamiltonian of a harmonic oscillator in terms of the ladder operators if

1
â = √ (p̂x + iµωx̂). 4
2~µω
7. The Jahn-Teller Effect states that highly symmetric nonlinear molecules tend to break degeneracy
by lowering symmetry. Show that degeneracy is indeed broken by considering the energy of
symmetric three dimensional box with one particle subjected to a slight change the dimension
of the box. 3

8. Identify H (0) and H (1) for the following problems: 1×2

(a) An oscillator governed by the potential

kx2 γx3 bx4

U (x) = + +
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(b) A hydrogen atom in an electric field of strength ε. The Hamiltonian operator for this system is

~2 2 e2
Ĥ = − ∇ − + eεrcosθ
2µ 4π0 r
9. Answer any one from following: 1×4=4
(a) Derive the first order correction to energy and wave function of a nondegenerate system using
time independent perturbation theory.
(b) Derive the explicit expression for the coeeficient of an initially unoccupied state of many level
systems using variation of constant technique.
2
10. Find the optimum form of the trial function e−κr and the upper bound to the ground state energy
of a hydrogenic atom. 4

11. Calculate the first order correction to the ground state energy of an anharmonic oscillator having
potential of the form 3
1 1 1
V (x) = kx2 + γx3 + bx4 .
2 6 24

12. Answer any one from following: 1×4=4

(a) What is a product wavefucntion? What is Pauli anti-symmetry principle? Construct the
Slater determinant of a three electron system and provide necessary justification for its
acceptance. 1+1+2
(b) What is Börn-oppenheimer approximation? Write the Hamiltonian of a system where there
are N-electrons and M-nuclei. What do you mean by normal and anomalous Zeeman effect?
2+2
13. Construct a diagram showing the form of the Zeeman effect when a magnetic field is applied to a
3
D2 −→3 P1 transition. 2

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