CHEM 327 (Quantum Chemistry-I)

Homework 2 (Due date: 20/10/2023)

1. Solve the Schrodinger’s Equation for particle in an infinite box potential centered in x=0. This
means that V(x)=0 for -L/2 ≤ x ≤ L/2, and V(x) is infinite elsewhere. (Note that your solution
and energies should be same as our solution, since this is only a shifting the potential by L/2,
physics is not changed!) (20 pts)

2. For the particle in a box system in the ground state, calculate the expectation values of x, x2,
p and p2. Check that the uncertainty principle holds for this system. ∆𝑥∆𝑝 ≥ ℏ/2 (15 pts)

3. Show that the states of particle in a box are orthogonal. (∫ Ψ𝑛 (𝑥)Ψ𝑚 (𝑥)𝑑𝑥 = 0 𝑖𝑓 𝑛 ≠
𝑚 𝑎𝑛𝑑 ∫ Ψ𝑛 (𝑥)Ψ𝑚 (𝑥)𝑑𝑥 = 1 𝑖𝑓 𝑛 = 𝑚 ) (15 pts)

4. A particle in the infinite square has the initial wave function,

Ψ(𝑥, 0) = 𝐴𝑥(𝐿 − 𝑥)
a. Normalize the wave function. (find A in terms of L). Plot this wave function. (5 pts)
b. Note that we can express the wave function in terms of the summation of pure states of particle
in a box.
∞

Ψ(𝑥, 0) = ∑ 𝑐𝑛 𝜑𝑛
1

What is cn for n=1, 2 and 3. Which state carries the largest coefficient? Does that make sense?
(10 pts)
c. If you measure the energy at t=0, what is the most likely answer you will get? (5 pts)

5. A particle is initially given with the following superposition of first two states of the particle
in a box potential:
1
Ψ(𝑥, 0) = [𝜓1 (𝑥, 0) + 𝜓2 (𝑥, 0)]
√2
a. Construct the generalized wave function with time evolution: Ψ(𝑥, 𝑡). (5 pts)
b. For this wave function, what is the probability for an energy measurement to be the ground state
energy for particle in a box (E1)? What is this probability for E2 and E3. (5 pts)
c. Calculate the expectation value of the energy, 〈𝐸〉 for this wave function. (Note that you can do
this in two different ways; the easy way and the hard way) (5 pts)
d. Calculate the probability distribution, 𝑃(𝑥, 𝑡) = |Ψ(𝑥, 𝑡)| 2 . Be careful! Because the wave
function is a superposition, not all time-dependent terms cancel out and you will get a time
dependence for the probability distribution. What is the period T of this superposition
distribution meaning the system return to its original position at t=0. (10 pts)
 𝑇 𝑇 3𝑇
e. Plot (Use Excel or some other graphics software) 𝑃(𝑥, 𝑡) 𝑡 = 0, 4 , 2 , 4
𝑎𝑛𝑑 𝑇. (10 pts)
f. Calculate the probability of finding the particle between x=0 and x=L/2. (If this was a stationary
state meaning pure ground state or first excited state, this will be simply 0.5”, however, your
answer will have a time dependence thanks to superposition) Plot this probability with respect to
t from t=0 to t=3T. (5 pts)