Quantum Chemistry Questions

Unit 1: SHO
1. Zero-point energies are a manifestation of the uncertainty principle. On the basis of this
statement explain why zero-point energy of SHO can’t be zero whereas that of rigid rotator
can be zero. (2017)
2. A particle of mass m, attached to a flexible spring is undergoing simple harmonic
oscillations. (2017)
(i) Give the expression for energy based on quantum mechanical treatment.
(ii) Find the expression for E.
(iii) Plot the wavefunction and probability density curves for  =0, 1 and 2.
What is the position at which the particle spends the maximum time in the ground state?
Compare this observation with the classical mechanic behavior.
3. Discuss Bohr correspondence principle with respect to the behavior of wave function of
SHO. Illustrate using its probability density plots. (2018)
4. Set up Hamiltonian operator for a particle oscillating about a mean position (SHO). Explain
the significance of zero-point energy of a simple harmonic oscillator. (2018)
5. Set up the Hamiltonian operator for a particle oscillating about a mean position (a simple
harmonic oscillator). Explain the significance of zero-point energy of a simple harmonic
oscillator. (2022)
6. Construct the Hamiltonian operator for Simple Harmonic oscillator and write the
Schrodinger equation. What is the zero-point energy of this type of system? (2023)
7. Evaluate the expectation values of <x> and <p> for the ground state of the harmonic
oscillator. (2018)
Given: Normalized wavefunction:
𝟏/𝟐
𝒂 𝒂𝒙𝟐
−
𝚿 (√ ) 𝒆 𝟐
𝝅

Standard integral
∞
𝟐 𝟏 𝝅 𝟏/𝟐
∫ 𝒙𝟐 𝒆−𝒂𝒙 . 𝒅𝒙 = ( )( )
−∞ 𝟐𝒂 𝒂

8. Determine the value of x at which the ground state wavefunction,  for the harmonic
oscillator exhibits a maxima. (2018)
Given:
𝒂 𝟏/𝟒 −𝜶𝒙𝟐
𝚿 = ( ) 𝒆𝒙𝒑 ( )
𝝅 𝟐
Unit 1: 1D Box
1. A particle of mass m, is confined to a two-dimensions region having dimensions, 0  x  a
and 0  y  b. The potential energy inside the box is zero and is infinity at the boundaries
of the box. Write the expression for the operator, wavefunction, nx ny (x, y) and energy,
En1 nv for the system. (2017)
2. State the variation theorem. Let the particle in a box be represented by the function
1 = x2 (1-x)2, Applying the variation theorem to the function calculate the ground state
energy (V=0 for 0  x  1 and V=  elsewhere) and the percentage error. Given the actual
ℎ2
𝐸𝑜 = 8𝑚𝑙2 does this function satisfy the variation theorem? (2017)
3. A particle of mass 10-6 kg is rolling on the smooth floor of a 1  10-4 m wide box with a
speed of 3.3313  10-3 ms-1. Applying the problem of particle is a 1 D box, calculate the
quantum number corresponding to the translational energy of the ball. Will you consider
the energy to be quantized in a practical sense? (2017)
4. Find the expectation values of (i) x (ii) px (iii) px2 for a particle of mass m, in a one-
dimensional box length l, having the solution, (2018)

𝟐 𝒏𝝅𝒙
𝚿𝒏 = √ 𝒔𝒊𝒏 ( )
𝒍 𝒍
Give the physical significance of each expression.
5. Prove that the solutions with n = 1 and n = 2 for a particle in a box are orthogonal to each
other. (2018)
6. Benzene may be taken as a two-dimensional box of edge length 0.4 nm consisting of six 
electrons. Calculate the energy required for the promotion of an electron from the ground
to the first excited state of benzene. (2018)
7. Show that the probability of finding the particle in a 1D box in the region L/4 and 3L/4 is
1 (−1)𝑘
½ if n is even, and 2 + if n is odd (2018)
𝑛𝜋
8. A particle of mass m moves in a 3D-box of sides a, b, c. If the potential is zero inside and
infinity outside the box, give the expressions for the energy, eigenvalues and
wavefunctions for a particle in 3D-box. What is the zero-point energy of the system? What
is the degeneracy of the first and second excited states? (2018)
9. A particle of mass m, in a 1D box of length a can be represented by the function, (2022)

𝒏𝝅𝒙
𝚿𝒏 = 𝒔𝒊𝒏
𝒂

̂𝑥2.
(n = 1,2,3…) Normalize the given function and find it is an eigen function of (i) 𝑃̂𝑥 (𝑖𝑖) 𝑝

10. A particle of mass, m, in a one-dimensional box of length a can be represented by the

following normalized trial wave function where N is the normalization constant. (2022)
𝚿𝒕𝒓𝒊𝒂𝒍 = 𝑵{𝒙(𝒂 − 𝒙)}
 (i) Calculate the expectation value of energy (E), of this particle in the ground state
using the trial wave function. (2022)
(ii) Compare this energy with the actual energy. Calculate the percentage error. (2022)
(iii) Is the trial wave function acceptable? Explain on the basis of variation theorem.
(2022)
11. The uncertainty in a quantity, represented by operator A is given as under, (2023)
𝝈𝟐𝑨 = 〈𝑨𝟐 〉 − 〈𝑨〉𝟐
For a particle in the ground state of a 1D box having length, L, represented by,
1⁄
2 2 𝜋𝑥
Ψ=( ) 𝑠𝑖𝑛 ( )
𝐿 𝐿
Determine x p where x and p represent position and momentum, respectively.
Use standard integral,
𝜋𝑥 𝐿2
∫ 𝑥 𝑠𝑖𝑛 ( 𝐿 ) = 4

And

𝜋𝑥 𝐿 3 4𝜋 3
∫ 𝑥 2 𝑠𝑖𝑛2 ( )=( ) ( − 2𝜋)
𝐿 2𝜋 3

12. Demonstrate that the Eigen functions for the particle in 1D box are orthogonal. (2023)
𝟏⁄
𝟐 𝟐 𝒏𝝅𝒙
𝚿(𝐱) = ( ) 𝒔𝒊𝒏 ( )
𝑳 𝑳
13. Write Hamiltonian operators for a particle moving under constant potential 'V' in a (i) one-
dimensional box and (ii) three-dimensional box. (2023)
14. As a crude treatment for the  electrons of a conjugated polyene, the  electrons of the
conjugated chain are considered as moving in a one-dimensional box across the end to end
conjugated chain. Considering 1,3-butadiene as a one-dimensional box of box length, 7.0
Å, calculate the wavelength of light absorbed when a  electron is excited from the highest-
occupied to the lowest- vacant level of the molecular electronic ground state. (2023)

Unit 1: Rigid rotator

1. A rigid rotator consists of two particles of mass m1 and m2 joined by a rigid rod of length
r. Based on classical considerations, show that the total energy of a rigid rotator is L2/2I,
where L is angular momentum and I is moment of inertia. How does this result differ from
quantum mechanical result? (2018)
 2. Starting from the expression for total energy of a rigid rotator, setup the Schrodinger
equation for the system in Cartesian coordinates. (2022)

Unit 2: Hydrogen Atom

1. Evaluate the expectation value of radius at which the electron in the ground state of
hydrogen atom (Z=1) is found. Given the wave function for this state is(2017)
𝟑
𝒛 𝟐 −𝟐𝒓
𝟏
𝚿𝟏,𝟎,𝟎 = ( ) 𝒆 𝒂𝒐
√ 𝒂𝒐
𝝅
Where ao is Bohr radius and,
𝒂
𝒏!
∫ 𝒓𝒏 𝒆−𝒂𝒓 𝒅𝒓 =
𝒂(𝒏+𝟏)
𝟎

2. Sketch R(r) and 4r2R2(r) vs r/ao for 3s orbital for hydrogen atom. Calculate the number
of radial nodes in the orbital. (2017)
3. Explain the significance of Born-Oppenheimer approximation. Write the Hamiltonian
operator for hydrogen atom using Born- Oppenheimer approximation. (2018)
4. Sketch R(r) and 4r2R2(r) vs r/ao for 3p orbital for hydrogen atom. Calculate the number of
radial nodes in this orbital. (2018)
5. Normalize the given wave function: (2018)
𝚽𝒎 = 𝐞𝐱𝐩(𝒊 𝒎 𝝓)
What is the significance of quantum number m with respect to hydrogen atom?
6. Plot the radial functions and radial probability distribution functions for an electron in
electron in hydrogen atom for all wave functions having n =2. Write the number of nodes
in each case. (2022)

7. Evaluate the expectation value of the radius 〈𝑟〉, at which the electron in the ground state
of Hydrogen atom (Z=1) is found. Given the wave function for this state is, (2022)
3
1 𝑧 2 −𝑍𝑟
Ψ1,0,0 = ( ) 𝑒 𝑎𝑜
√𝜋 𝑎𝑜
Where ao is the Bohr radius, and
∞
𝑛!
∫ 𝑟 𝑛 𝑒 −𝑎𝑟 𝑑𝑟 =
0 𝑎(𝑛+1)
8. By applying the procedure of separation of variables on the following Schrodinger equation
for an electron in a hydrogen atom, derive three equations, one dependent on variable, r,
second dependent on variable,  and third dependent on variable, . In this equation (r,,
 ) is the function of three independent variables r, , and . Considering (r,, ) = R(r)
* ()*(), (2022)
ℎ2 𝑑 2 𝑑 1 𝑑 𝑑 1 𝑑2 𝑍𝑒 2
[− 2 2 { (𝑟 )+ (𝑠𝑖𝑛𝜃 ) + }− ] Ψ = 𝐸Ψ
8𝜋 𝜇𝑟 𝑑𝑟 𝑑𝑟 𝑠𝑖𝑛𝜃 𝑑𝜃 𝑑𝜃 𝑠𝑖𝑛2 𝜃 𝑑Ψ2 𝑟

9. Using normalized ground state wave function for hydrogen atom (2023)
3
1 ⁄2 (− 𝑟 )
Ψ(r) = 2 ( ) 𝑒 𝑎
𝑎
Determine (i) 〈𝐸〉 (ii) The radius of maximum radial density distribution of electron.

10. Why do we need to employ approximate methods to determine solution for multielectron
atoms? Explain Variation principle as an approximate method to determine approximate
wavefunction. (2023)
11. Write the Hamiltonian for hydrogen (molecule) and explain each term. (2018)
12. Write the complete Hamiltonian operator for Li atom explaining all the terms. Write the
modified Hamiltonian operator after applying Born Oppenheimer approximation. (2022)
13. Calculate the average distance of the electron from the nucleus of H atom in the 2s state
(2018)

𝟑
𝟏 𝟏 𝟐 𝒓 − 𝒓
𝚿𝟐𝟎𝟎 =( ) ( ) (𝟐 − ) 𝒆 𝟐𝒂𝒐
√𝟑𝟐𝝅 𝒂𝒐 𝒂𝒐
Given:

∞
∫ 𝒓𝒏 𝒆−𝒂𝒓 𝒅𝒓
𝟎
𝒏!
=
(𝒂)𝒏+𝟏
14. Write short notes on
(a) Born Oppenheimer approximation
(b) Variation Principle

15. Determine the energy of H atom using the trial wave function  = e-ar where a is an
adjustable parameter and r is the distance of the electron from the nucleus. (2018)
Given:
∞
𝒏!
∫ 𝒓𝒏 𝒆−𝒂𝒓 𝒅𝒓 =
𝒂(𝒏+𝟏)
𝟎
Unit 3: Chemical bonding
1. Write the LCAO-MO trial wave function of H2+ using molecular orbital approach. Derive
the expressions for molecular orbital wave functions corresponding to the bonding and
anti-bonding energy levels of H2+.(2017)
2. Sketch the bonding and antibonding molecular orbitals of H2+.(2017)
3. Molecularity orbital theory gives equal weightage to covalent and ionic structure whereas
valence bond theory ignores ionic character. Explain using the trial wave function of H2
molecule. (2018)
4. Write down the normalized valence bond wavefunction and molecular orbital
wavefunction for H2 molecule. Compare the expressions obtained and explain
configuration interaction. (2018)
Arrive at the following expression for 𝐻2+ :
∝ +𝜷
𝑬+ =
𝟏+𝑺
(Where  is the coulomb integral,  is the resonance integral and S is the overlap integral)
using LCAO-MO treatment.
5. For a one-electron homonuclear diatomic molecule the values of some relevant integrals
are given below: (2018)
̂ 𝚽𝑨 𝒅𝝉 = −𝟑𝒂. 𝒖.
∫ 𝚽𝑨 𝑯

̂ 𝚽𝑩 𝒅𝝉 = −𝟑𝒂. 𝒖.
∫ 𝚽𝑩 𝑯
𝟑
∫ 𝚽𝑨 𝑯̂ 𝚽𝑩 𝒅𝝉 = − 𝒂. 𝒖.
𝟐
𝟏
∫ 𝚽𝑨 𝚽𝑩 𝒅𝝉 = − 𝒂. 𝒖.
𝟐
Where A and B are the normalized set of basis functions for an LCAO wavefunction.
Find the energy of the bonding molecular orbital and find the normalized wavefunction.
6. If A and B are two atoms bonding along the z-axis, predict giving reasons which of the
following orbitals can combine: (2018)
(i) 2s(A) and 2pz(B)
(ii) 1s(A) and 2s(B)
 General questions (Operators, Hermitian operator, Commutation,
Normalization, Orthonormal, Eigen values Eigen function, function acceptability)

1. If 1 & 2 are eigenfunctions of linear operator Ȃ with the same eigen value a, then show
that any linear combination of 1 & 2 will also be an eigenfunction of Ȃ having the same
eigen value. (2017)
2. Determine whether the following wave-functions are acceptable or not as state functions
over the indicated interval: (2017)
(i) exp(-x) 0x 
(ii) exp(-x) -  x  

3. What are orthonormal functions? Show that the set of functions: (2017)
𝟏
𝚽𝒎 = 𝒆𝒙𝒑(𝒊 𝒎 𝝓) 𝒇𝒐𝒓 𝟎 ≤ 𝝓 ≥ 𝟐𝝅 are orthonormal.
√𝟐𝝅

4. Evaluate [𝐿̂𝑥 , 𝐿̂𝑦 ](2017)

5. For a particle of mass, m in a cube of edge length 1, the energy of a quantum level is found
𝒉𝟐
to be, 𝑬𝒐 = 𝟏𝟒 .Calculate the quantum numbers and fin the degeneracy
𝟖𝒎𝒍𝟐
corresponding to this level. (2017)
6. Normalize the wavefunction x(a-x) over the range 0  x  a. (2017)
𝑑2 𝑑2
7. Determine whether or not the operators 𝑥 2 𝑑𝑥 2 𝑎𝑛𝑑 commute. What is the significance
𝑑𝑥 2
of communication? (2018)
8. What is accidental degeneracy? Explain with an example. (2018)
𝑑2
9. Define Hermitian operator. Show that 𝑑𝑥 2 is a Hermitian operator. (2018)
10. Under what conditions, the wave function  is said to be an acceptable wave function?
What is the physical significance of 2 (2018)
11. The term state and energy level are not synonymous in wave-mechanics. Explain. How
many states and energy levels lie in the energy range of E< 10h2/8ml2? (2018)
12. The function given below are defined in the internal x = -a and x=+a as follows:
F(x) = N(a2-x2)
Assuming the value of the function to be zero for x<-a and x>+a, calculate the
Normalization constant N. (2018)

13. Show that the Morse potential:

V = D[1- exp {a(req-r)}]2
Is reducible to harmonic potential for the lower vibrational levels. Also show that the force
constant is give as k = 2Da2(2018)

14. What do you understand by the term transition probability? Depict the energy levels and
probability densities for the first four levels of a harmonic oscillator with the help of a
diagram. (2018)
15. Show that if two operators A and C are Hermitian, then their product (AC) is also Hermitian
if and only if A and C commute. (2018)
16. Find the commutator of the position and momentum operator and give its physical
significance, giving the name of the principle it verifies. (2018)
17. Discuss the postulates of quantum mechanics. (2022)
18. Show that the eigenvalues of a Hermitian operator are always real. (2022)
19. Giving reason, state which of the following are acceptable wave functions in the indicated
interval. (2022)
(i) Sin x (0, 2)
-x
(ii) e (-, +)
(iii) 1/x (0, )
-1
(iv) Sin x (-1, 1)

20. Prove that the functions having different real eigen values for linear momentum operator
are orthogonal. (2023)
𝑑
21. Starting from [𝑑𝑥 , 𝑥] = 1, use the commutator identities to find (2023)
(i) ̂𝑥2 ]
[𝑥̂ , 𝑝
(ii) ̂ ], 𝐻
[𝑥̂ , 𝐻 ̂ is Hamiltonian for a one-particle, three-dimensional system.

22. A molecule X has 10 pi electrons and it is assumed to have cubical shape with edge length
10 pm. Give the quantum numbers corresponding to the highest occupied energy levels.
Based on the free electron model, calculate the longest wavelength required for transition.
(2023)
23. Normalize the following function: (2023)
(i) 𝑓(𝑟) = 𝑟 𝑒 (−𝑎𝑟) 0≤𝑟 ≥ ∞
(ii) 𝑓(Ψ) = 𝑁 𝑒 (𝑖𝑚ϕ) 0 ≤ Ψ ≥ 2𝜋
24. Using linear momentum operator 𝑝 ̂𝑥 , 𝑝
̂𝑦 𝑎𝑛𝑑 𝑝
̂.
𝑧 Derive angular momentum operators,
ℎ 𝑑
̂𝑥 , 𝐿̂𝑦 𝑎𝑛𝑑 𝐿
𝐿 ̂𝑧 . 𝑈𝑠𝑖𝑛𝑔 𝐿
̂𝑧 = −𝑖 ( ) construct the Schrodinger equation dependent on
2𝜋 𝑑𝜙
variable 𝜙 only. Write a possible solution as an eigen function and determine eigen values.
(2023)