Department of Chemistry CH104

Gauhati University Practice Set 2.

Quantum Chemistry - CH104 Quantum Chemistry
M.Sc, I Sem Solve as you wish

1. The kinetic energy operator of the H-atom in polar coordinates is given by

−~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

(a) State the physical significance of each of the three summated terms.
(b) Identify which terms in the above equation leads to the quantum numbers n, l and m.
(c) What are their corresponding energies and wavefunctions.
(d) Justify if the spin quantum number can be identified from the above eqution.

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

3. Using the Rodriguez formula, evaluate the first 3 Hermite polynomials. Then, write down the
corresponding wavefunctions (unnormalized) and sketch the probabilities.

4. Explain the logic behind assuming the solution for the wavefunction of a harmonic oscilator: i.e
2
why do we assume the solution to be, ψ(z) = h(z) × e−βz

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

1
i) â = √ (p̂x + iµωx̂).
2~µω
1
ii) â = √ (ip̂x + µωx̂).
2~µω
iii) Evaluate the commutator [â, ↠] for each of the above cases.

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

p
15/4 2z 2 − (x2 + y 2 )
ψ= √ p (6 − ρ)ρ2 e−ρ/2 , ρ = 2Zr/ao
96 5 (4π) r2

(a) How many nodes are present?

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

7. Using the mathematical expressions for the 2s and 2px orbitals, explain why the 2s and 2px orbitals
have different penetrating abilities.

8. Using the 2pz atomic orbital as basis set in the CH2 CH2 molecule, mathematically setup the
Hamiltonian operator in matrix form and obtain the energy. Explain what is meant by Coulomb
integral and resonance integrals in this Hamiltonian.

©HPG P.T.O. . .
Chemistry Quantum Chemistry 2/2
9. Using the 2pz atomic orbital as basis set, find the stabilization energy for the allyl radical in terms
of the delocalization integral, β. Write down the corresponding wavefunctions for each energy
state in terms of the 2pz basis orbital.
10. Quantitatively explain the tunneling phenomena from the particle in a box model and find a simple
expression for the tunneling probability.
11. An electron having total kinetic energy E = 4.50eV approaches a rectangular energy barrier with
V = 5.00eV and L = 950pm. Classically, the electron cannot pass through the barrier because
E < V . Calculate probability of tunneling of this electron through the barrier.

©HPG End