Problem set for 4th week of the course Quantum Physics 1

(version 2023/2024)

Homework, to be made before/after the tutorial:

From the book – Chapter 2 – 2.29, 2.34, Chapter 3 – 3.1, 3.3, 3.5, and problems W4.2 – W.4.3 of this
handout.

Problems to work on during tutorial:

Problem W4.1 (this handout) and Chapter 2, problem 2.33. This is the minimum set to be completed
during the tutorial.

Other good problems that we selected (we advise you to make these for the topics where you need or
like to do extra training):
Chapter 2 –2.43, 2.47 and Chapter 3 – 3.2, 3.4, 3.6.

Problem W4.1
In a molecule, an electron is tightly bound to the other particles in the system. In one direction, however,
it is free to move a little bit from one atom to a neighboring atom. Along this direction, the electron
experiences a one-dimensional potential V(x) as a function of position x. The potential V(x) can be
approximated very well by the potential landscape as in the following sketch.
V=∞ V=∞

V = V0

V=0
x
-a 0 a
region 1 region 2 region 3 region 4

a) Give the Hamiltonian for this system, with the potential V(x) written out for each region along x.

b) It turns out that the energy for the ground state of this system Eg > V0. Consequently, a general form
for the part of the wavefunctions of the energy eigenstates in region 2 will be ϕ 2 ( x ) = Ae
ik 2 x
+ Be − ik 2 x
, while for region 3 it will be ϕ3 (x ) = Ceik x + De−ik x . In regions 1 and 4 the wavefunctions will be
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zero. Explain why this can be assumed for regions 1, 2, 3 and 4 (see also question c).

c) Give expressions for k2 and k3. Show how these expressions can be derived from the time-independent
Schrödinger equation.

d) To find the energy eigenvalues and eigenfunctions of this system, one needs to write down equations
that can be used to solve for A, B, C and D. Explain how one can define the set of equations needed to
solve this problem and give these equations (do not worry about normalization of the eigenstates yet).

e) Show that working out this problem of d) is equivalent to solving the following linear algebra problem:
 
Mv = s , with

 1 1 −1 −1   A 0
     
 ik − ik2 − ik3 ik3   B  0 .
M =  − ik22 a , v =  , s = 
e eik 2 a 0 0 C 0
     
 0 0 eik 3 a e− ik 3 a   D 0
    

f) Use qualitative reasoning to find out what the shape is of the wavefunction for ground state and the
first excited state as a function of x. Draw a sketch for these two wavefunctions and explain your
answer. Hint: consider this system as the result of two coupled particle-in-a-box systems, where the
width of the tunnel barrier between the two boxes is reduced to zero, and the degeneracy of the two
boxes is lifted. Also use the answer on c) if needed.

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Problem W4.2
In this problem you practice quantum mechanical calculation on systems that can be represented by 2x2
matrix representations.
In a diatomic molecule, like H2, the electron feels the attraction of the nuclei. A good approximation for
the potential landscape is sketched below.

Potential

-a 0 a
Position

The barrier between the two wells is so high, that the tunneling between the left and right well is
negligible. In this situation, the system has two energy eigenstates with the same energy E0. One of these
states, denoted as |ϕL〉, corresponds to the particle being localized around –a in the left well. The other
energy eigenstate, denoted as |ϕR〉, corresponds to the particle being localized around +a in the right well.
All other energy eigenstates are so high in energy that they do not need to be considered. The system can
therefore be described as a two-state system. It is then convenient to use a matrix and vector
representation that uses |ϕL〉 and |ϕR〉 as basis vectors, which gives the following relations (Ĥ0 is the
Hamiltonian):
�0 = �𝐸𝐸0
𝐻𝐻
0 1 0
�, |𝜑𝜑𝐿𝐿 ⟩ = � �, |𝜑𝜑𝑅𝑅 ⟩ = � �.
0 𝐸𝐸0 0 1
When the molecule is placed in a static electric field of 1 V/nm, the only effect on the potential for the
electron is that the barrier between the two wells becomes lower. In that case tunneling between the two
wells can no longer be neglected when describing the dynamics of the electron. Using the same matrix
notation as before (also in the same basis), the Hamiltonian of the system is now (here T is a real and
negative number):
�0 = �𝐸𝐸0
𝐻𝐻
𝑇𝑇
�.
𝑇𝑇 𝐸𝐸0
For the rest of the problem, assume that the static electric field is on!

a) From symmetry arguments it is known that the energy eigenstates of the Hamiltonian Ĥ are symmetric
and anti-symmetric superpositions of |ϕL〉 and |ϕR〉, which are (using the same basis and vector notation
as in the above expression)
 1   1 
 2  and  2.
 1   1 
  − 
 2  2

Here, one of these vectors is the ground state |ϕg〉 and the other the excited state |ϕe〉
Calculate the energy eigenvalues Eg and Ee that belong to these energy eigenvectors, and show which
eigenvector is the ground state and which one is the excited state.

b) Prove that these energy eigenstates of Ĥ are normalized and orthogonal.

c) There is an operator (observable) Â for the position of the electron in this double well system,
− a 0
Aˆ ↔   .
 0 a
Calculate whether  commutes with Ĥ0, and whether  commutes with Ĥ.

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d) What are the eigenvectors and eigenvalues of Â?

e) There is an experimental apparatus that can measure the physical property described by  (determine
whether the electron is in the left or the right well by performing a measurement of a short time). For the
case that the system is in the ground state of Ĥ, discuss what the possible measurements outcomes are,
derive the probability for each of the measurement outcomes, and what the state is immediately after the
measurement for each of the measurement outcomes.

f) Repeat question e), but now for the case that the system is at the moment of measurement in the state
1 2
Ψ = ϕg + ϕe .
3 3

g) The outcome of a measurement of  (which ended at time t = 0) is that the particle is in the left well.
Express the state at t = 0 in terms of state |ϕg〉 and |ϕe〉.

h) Calculate the value of the four quantities

ϕ g Aˆ ϕ g , ϕe Aˆ ϕe , ϕ g Aˆ ϕe and ϕe Aˆ ϕ g .
Describe in words what these quantities represent.

i) Following up on question g) and h), calculate how  depends on time for t > 0. Describe in words
what the calculation represents.

Problem W4.3
Suppose an operator  has an eigenfunction φ1 with eigenvalue a1. It is non-degenerate: there are no
other (linearly independent) eigenfunctions having eigenvalue a1. An operator B̂ commutes with  ,
which is usually written as [ Aˆ , Bˆ ] = 0 .

a) Show that φ1 is also an eigenfunction of B̂ .

Hint: Show that Bˆ ϕ1 is an eigenfunction of  , and use the fact that φ1 is non-degenerate.

Now suppose there are two linearly independent eigenfunctions of  : φ1 and φ2, each having
eigenvalue a. Any linear combination c1 φ1 + c2 φ2 is an eigenfunction of  corresponding to
eigenvalue a, so now all we can say is that Bˆ ϕ1 and Bˆ ϕ 2 are linear combinations of φ1 and φ2. Note
that φ1 and φ2 are not necessarily also eigenfunctions of B̂ .

However, it can be shown that when an operator  has n linearly independent degenerate
eigenfunctions, one can form n linear combinations that are also eigenfunctions of B̂ (if  and B̂
commute).

Let’s apply this to a free particle in one dimension.

b) Show that the Hamiltonian of a free particle commutes with the momentum operator.

 2k 2
The functions cos(kx) and sin(kx) are eigenfunctions of the Hamiltionian (with energy ), but not
2m
of momentum.

c) Show that you can indeed create 2 different linear combinations of cos(kx) and sin(kx) that are
eigenfunctions of p̂x .

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