# Physical chemistry (quantum) hw

2023/01/19Chem 113A Problem Set 02: Lectures 04β05

Due 2023/01/26 @ 10 PM

We encourage you to work with others in the class on the problem set, but the end product must represent your

effort. Useful integrals can be found on the last page.

Part 1 (To be done in Discuss Section. If you do not finish it in section, please finish at home)

1) Particle in a finite box

For a particle in a finite box, where the potential energy outside the box do not go to infinity, the

wavefunction does not go to zero at the edge (as shown in the picture above). For particle in a finite box,

the potential energy is described as

πΏ

πΏ

0, β β€ π₯ β€

π(π₯) = {

2

2

π0 , otherwise

πΏ

The center of the box is at π₯ = 0 and the edge of the box is at π₯ = Β± 2. In this situation, the wave function

for the ground state (n=1) is

π(π₯) = π΄π βπ|π₯|

where

2π(π0 β πΈ)

π=β

β2

π0 is the potential energy outside the box, πΈ is the energy of the particle, and πΈ < π0
a. Set up the integral that calculates the probability of finding the particle inside the box.
pg. 1
Problem Set 02
Due 01/26
b. The probability of finding the particle inside the box plus the probability of finding the particle outside the
box equals one, because the particle must be either inside or outside the box. Express the probability of
finding the particle outside the box in terms of your answer from part a.
c. To deal with the absolute value, weβll use the following relation
π
π
β«π
βπ|π₯|
βπ
ππ₯ = 2 β« π βππ₯ ππ₯
0
Calculate the probability of finding the particle outside the box in terms of π΄, π, and πΏ
π΄2
Note: Using the normalization condition, π = 1 (You can try to prove to yourself that this is true.)
d. For classical physics, if the potential energy at the edge of the box (U0) is greater than the energy of the
particle, is it possible for the particle to be outside the box? What about quantum mechanics?
pg. 2
Problem Set 02
Due 01/26
e. What happens to the probability of finding the particle outside the box as π0 goes to infinity?
2) Operators Evaluate π = π΄Μπ, where π΄Μ and π are given below:
3
π
a. π΄Μ = ππ₯ 3 ; π = π βππ₯
1
b. π΄Μ = β«0 ππ₯ ; π = π₯ 3 β 2π₯ + 3
π
π
π
c. π΄Μ = ππ₯ + ππ¦ + ππ§ ; π = π₯ 3 π¦ 2 π§ 4
pg. 3
Problem Set 02
Due 01/26
3) Superposition of Particle in a 1-D Box For a particle in a box, supposed our particle is described as the sum
of the π = 1 wavefunction and the π = 2 wavefunction:
π(π₯) = π1 ππ=1 (π₯) + π2 ππ=2 (π₯)
where
2
ππ
ππ = β sin ( π₯)
πΏ
πΏ
a. Furthermore, letβs say π1 = π2 .
2
π
2
2π
π(π₯) = π1 β sin ( π₯) + π1 β sin ( π₯)
πΏ
πΏ
πΏ
πΏ
Normalize the wavefunction π(π₯)
Useful Integrals
πΏ
π
2π
β« sin ( π₯) sin ( π₯) ππ₯ = 0
πΏ
πΏ
0
πΏ
ππ
πΏ
β« sin2 ( π₯) ππ₯ =
πΏ
2
0
pg. 4
Problem Set 02
Due 01/26
Part 2 (Take-home)
1) Particle in a 2-D Box
In recent years, a lot of research have been focused on 2-D materials such as
perovskites, MoS2, or graphene sheet.
These materials are typically only a few atoms thick, so they can be modeled
as particle in a 2-D box. The Hamiltonian for a 2-D box is
Μ=β
π»
β2 π 2
π2
+
(
)
2π ππ₯ 2 ππ¦ 2
a. Show that
π(π₯, π¦) =
ππ¦ π
2
ππ₯ π
sin (
π₯) sin (
π¦)
πΏπ₯ πΏπ¦
πΏπ₯
πΏπ¦
is an eigenfunction of the 2-D Hamiltonian, where πΏπ₯ and πΏπ¦ is the length of the box in the x- and ydirections, respectively, and ππ₯ and ππ¦ are the quantum numbers. What is the energy for the particle in a
2-D box as a function of πΏπ₯ , πΏπ¦ , ππ₯ and ππ¦ .
pg. 5
Problem Set 02
Due 01/26
b. If our box is a square (πΏπ₯ = πΏπ¦ ), plot the energy level diagram for the first 8 energy levels for a particle in a
2-D box.
c. Use Figure 1 and Figure 2 on this website (half way down the webpage):
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplement
al_Modules_(Physical_and_Theoretical_Chemistry)/Quantum_Mechanics/05.5%3A_Particle_in_Boxes/Parti
cle_in_a_2-Dimensional_Box
to visualize the wave function for the first 8 energy levels. You can drag the surface plots to rotate and look
at the wave functions from different angles. From the energy level diagram, you see that (ππ₯ = 2, ππ¦ = 1)
and (ππ₯ = 1, ππ¦ = 2) are degenerate (i.e., they have the same energy). From the plots of the
wavefunctions, does it make sense that these two energy levels are degenerate?
pg. 6
Problem Set 02
Due 01/26
d. How can one break degeneracies for a particle in a 2-D box? (i.e., how can one make (ππ₯ = 2, ππ¦ = 1) and
(ππ₯ = 1, ππ¦ = 2) have different energies?
e. For a particle in a 2D-box, is it possible to measure its x-position and y-momentum simultaneously? In other
words, what is the uncertainty relationship Ξπ₯Ξππ¦ equal to?
π
π₯Μ = π₯; πΜπ¦ = βπβ
ππ¦
pg. 7
Problem Set 02
Due 01/26
2) Angular Momentum Operator The angular momentum operators are defined as followed:
π
π
π
π
π
π
πΏΜπ₯ = βπβ (π¦ β π§ ) ; πΏΜπ¦ = βπβ (π§
β π₯ ) ; πΏΜπ§ = βπβ (π₯
βπ¦ )
ππ§
ππ¦
ππ₯
ππ§
ππ¦
ππ₯
Μ
Μ
Μ
Μ
Μ
Μ
a. Calculate the following commutators, [πΏπ₯ , πΏπ¦ ], [πΏπ¦ , πΏπ§ ], and [πΏπ§ , πΏπ₯ ].
b. What do the commutators say about the ability to measure the components of angular momentum
simultaneously?
pg. 8
2023/01/18
Chem 113A Lecture 04: Wavefunctions and Operators
Objectives:
β’ Know what a wavefunction and an operator are.
o Suggested readings: 3.2, 3.3, 3.4, 3.6, 4.1, 4.2
o Suggested textbook problems: 3-1,3-2, 3-5, 3-6, 4-1, 4-2, 4-3, 4-5
Time-Independent SchrΓΆdinger Equation
Μ Ξ¨ = πΈΞ¨
π»
Postulate 1 The state of quantum-mechanical system is completely specified by a function
Ξ¨(π, π‘) that depends on the coordinates of the particle and on time. This function, called the
wavefunction of state function, has the important property that Ξ¨ β (π, π‘)Ξ¨(π, π‘)ππ₯ππ¦ππ§ is the
probability that the particle lies in the volume element ππ₯ππ¦ππ§ located at π and at time π‘.
Particle-in-a-box:
Page 1
Lecture 04
2023/01/18
Example What is the probability of finding the particle between π₯ = 0 and π₯ = πΏ/4 for the
ground state of a particle-in-a-box?
Useful integral
πΏ/4
πππ₯
πΏ
πΏ
ππ
) ππ₯ = β
sin ( )
πΏ
8 4ππ
2
β« sin2 (
0
Two requirements for Postulate 1:
1. The wavefunction must be well behaved.
2. The wavefunction must be normalized.
Page 2
Lecture 04
2023/01/18
Example Let Ξ¨(π₯) = π β π₯, where β1 β€ π₯ β€ 1. Is Ξ¨(π₯) normalized? If not, normalized Ξ¨(π₯)
Postulate 2 To every observable in classical mechanics there corresponds a linear, Hermitian
operator in quantum mechanics.
Operator: a symbol that tells you to do something to whatever follows the symbol.
Example Let π(π₯, π‘) = cos(π‘) sin(π₯). Evaluate π΄Μπ(π₯, π‘), where π΄Μ is given below:
π
a. π΄Μ = ππ₯
π2
π
c. π΄Μ = ππ₯ 2 + ππ‘ + 3
b. π΄Μ = π₯
Page 3
Lecture 04
2023/01/18
Linear Operator
An operator is linear ifβ¦
Example Determine whether the following operators are linear or nonlinear:
a. π΄Μ = π/ππ₯
b. π΄Μ = SQRT
Order of operation with operators
π
Example Let π΄Μ = π₯, π΅Μ = ππ₯, and π(π₯) = sin(π₯). Perform the following operations:
a. π΄Μπ΅Μ π(π₯)
b. π΅Μ π΄Μπ(π₯)
c. π΅Μ 2 π(π₯)
Page 4
2023/01/20
Chem 113A Lecture 5: Commutator, Eigenfunctions, and Eigenvalues
Objective:
β Know how to calculate the commutator of two operators and what it means.
β Know how to identify whether a function is an eigenfunction of an operator.
β Know how to calculate eigenvalues given an eigenfunction and an operator.
o Suggested reading: 3.3 β 3.6, 4.3, 4.4
o Suggested textbook problems: 4-11 β 4-17
The Commutator of Two Operators
Example Evaluate the commutator [πΜπ₯ , π₯]
If two operators do not commute, then their corresponding observable quantities do not have
simultaneously well-defined values.
2
1
ππ΄2 ππ΅2 β₯ β (
4
β«
π β [π΄Μ, π΅Μ ]π ππ₯)
πππ π ππππ
Page 1
Lecture 05
2023/01/20
Example Use the commutator of the position operator and the momentum operator to derive
the Heisenberg uncertainty principle.
Postulate 3 In any measurement of the observable associated with the operator, π΄Μ, the only
values that will ever be observed are the eigenvalues π, which satisfy the eigenvalue equation
π΄Μππ = πππ
ππ
Example Is π ππ₯ an eigenfunction of ππ₯ π. If so, what is the eigenvalue?
Time-Independent SchrΓΆdinger Equation is an example of an eigenvalue/eigenfunction
problem.
Page 2
Lecture 05
2023/01/20
Particle-in-a-Box
Potential Energy
Boundary Conditions
Solving the SchrΓΆdinger Equation
Three Cases: πΎ = 0, πΎ > 0, and πΎ < 0
Case 1: πΎ = 0
Page 3
Lecture 05
2023/01/20
Particle-in-a-Box Solution
Page 4
2023/01/23
Chem 113A Lecture 06: Postulate 3, Hermitian Operators, Expanding Wavefunctions
Objective:
β Know the following terms: Hermitian operators, orthonormal, Fourier coefficients.
β Know how to expand a wavefunction in terms of a set of eigenfunctions.
β Know how to calculate the variance of an operator
o Suggested readings: 4.3 β 4.8
o Suggested textbook problems: 4-22 β 4-24
Postulate 3 In any measurement of the observable associated with the operator, π΄Μ, the only
values that will ever be observed are the eigenvalues, π, which satisfy the eigenvalue equation
π΄Μππ = πππ
Example: Particle-in-a-box
Hermitian Operators
Definition:
Why Hermitian operators are special?
Page 1
Lecture 06
2023/01/23
Example: Particle-in-a-box
An analogy using the Cartesian Coordinate
** The probability of obtaining a certain value of an observable in a measurement is given by
the Fourier coefficient **
Page 2
Lecture 06
2023/01/23
Example Expand
1
30 2
Ξ¨(π₯) = ( 5 ) π₯(πΏ β π₯), 0 β€ π₯ β€ πΏ
πΏ
in terms of the orthonormal complete set of eigenfunctions of a particle in a box.
πΏ
πππ₯
πΏ 3
β« π₯(πΏ β π₯) sin (
) ππ₯ = 2 ( ) [1 β cos(ππ)]
πΏ
ππ
0
If we measure the total energy of Ξ¨(π₯), what is the probability of obtaining πΈ = πΈπ=1 ?
Page 3
Lecture 06
2023/01/23
Example If we measure the total energy of ππ=1, what is the probability of obtaining πΈ =
πΈπ=2 ?
Postulate 3 and Uncertainty Principle If two operators commute, they have the same set of
eigenfunctionsβ¦
Page 4