ECE/MAT 211A: Midterm. Due February 21, 2018, at noon.

To be done individually.

NAME: _____________________________________________

Problem 1: Numerical Solutions for the Schroedinger Equation.

For general potentials, a common approach is to use a numerical method to solve the
Schroedinger equation, as analytic solutions may not be possible. For a 1D system, we can use
the finite difference method to approximate derivatives on an array of N equally spaced points.
𝑓𝑓(𝑥𝑥+∆𝑥𝑥)−𝑓𝑓(𝑥𝑥)
The first derivative of a function, 𝑓𝑓 ′ (𝑥𝑥) = lim , is approximated as
∆𝑥𝑥→0 ∆𝑥𝑥
𝑓𝑓(𝑥𝑥𝑖𝑖+1 )−𝑓𝑓(𝑥𝑥𝑖𝑖 )
𝑓𝑓 ′ (𝑥𝑥𝑖𝑖 ) = .
∆𝑥𝑥

𝑓𝑓(𝑥𝑥𝑖𝑖+1 )−2𝑓𝑓(𝑥𝑥𝑖𝑖 )+𝑓𝑓(𝑥𝑥𝑖𝑖−1 )

The second derivative is approximated as 𝑓𝑓 ′′ (𝑥𝑥𝑖𝑖 ) = ∆𝑥𝑥 2
.

The full Schroedinger equation is approximated by

ℏ2 𝜓𝜓(𝑥𝑥𝑖𝑖+1 )−2𝜓𝜓(𝑥𝑥𝑖𝑖 )+𝜓𝜓(𝑥𝑥𝑖𝑖−1 )
− 2𝑚𝑚 ∆𝑥𝑥 2
+ 𝑉𝑉(𝑥𝑥𝑖𝑖 )𝜓𝜓(𝑥𝑥𝑖𝑖 ) = 𝐸𝐸𝐸𝐸(𝑥𝑥𝑖𝑖 ) .

For this equation to accurately represent the system, it must hold for each 𝑥𝑥𝑖𝑖 , which lets us set
up a system of N equations, with one equation coming from each 𝑥𝑥𝑖𝑖 .

(−2)ℏ2 ℏ2
⎡− + 𝑉𝑉(𝑥𝑥1 ) − 0 …⎤
⎢ 2𝑚𝑚 2𝑚𝑚 ⎥ 𝜓𝜓(𝑥𝑥1 ) 𝜓𝜓(𝑥𝑥1 )
⎢ ℏ2 (−2)ℏ2 ℏ2 ⎥
⎢ − − + 𝑉𝑉(𝑥𝑥2 ) − …⎥ �𝜓𝜓(𝑥𝑥2 )� = 𝐸𝐸 �𝜓𝜓(𝑥𝑥2 )�
⎢ 2𝑚𝑚 2𝑚𝑚 2𝑚𝑚 ⎥ 𝜓𝜓(𝑥𝑥3 ) 𝜓𝜓(𝑥𝑥3 )
⎢ ℏ2 (−2)ℏ2 ⎥ ⋮ ⋮
⎢ 0 − − + 𝑉𝑉(𝑥𝑥3 ) …⎥
2𝑚𝑚 2𝑚𝑚
⎣ ⋮ ⋮ ⋮ ⋱⎦
From the matrix equation, it is clear that the permitted eigenvalues E are the eigenvalues of the
matrix to the left. Here we assume we are looking for bound states, and have implicitly defined
the boundary conditions of the wavefunction to go to 0 at 𝑥𝑥0 and 𝑥𝑥𝑁𝑁+1 .

We have provided a MATLAB code (Schrod.m) that implements the above. The only necessary
input parameters are the potential as a function of x, and we have provided sample potentials.

The code will output two variables, a vector E, which corresponds to the eigenstates of the
system, and a matrix Vec. The rows of the matrix Vec are the eigenvectors corresponding to the
energies. (i.e.: If 𝐸𝐸1 is the lowest energy of the system, than the first row of Vec is the ground
state eigenfunction of the system). The eigenfunctions are in general not normalized.

1
We call L the width of the well with infinitely high barriers (informally referred to as the “infinite
square well”); this is also the total width of the simulation area; w is the width of the well with
finite barrier height (“finite square well”); and V is the barrier height for the finite well.

1. Run the problem for the infinite square well potential. Determine an appropriate
method to normalize the wavefunction, and plot the unnormalized wavefunction, the
normalized wavefunction, and the analytical solution on the same plot.

2. Compare the first excited state of the Infinite square well with L = 10 Å to the first
excited state of the finite square well with L = 50 Å, w = 10 Å, V = 1 eV and the first
excited state of the well with L = 50 Å, w = 10 Å, V = 3 eV. What is the probability of the
particle materializing outside the well in each case?

3. We can apply this 1D problem to the hydrogen atom, as the radial equation takes the
form of a 1D potential in χ(r) = 𝑟𝑟𝑟𝑟(𝑟𝑟). On the same plot, compare the 3s, 3p, and 3d
orbitals of hydrogen. What is the expected value for 〈𝑟𝑟〉 and 〈𝑟𝑟 −1 〉 in each case?
(Hint: Consider numerical integration)

Additional information for downloading/using MATLAB:

1) Go to http://www.software.ucsb.edu/info/matlab and follow the steps outlined to

acquire a MATLAB license and install it on your computer. Alternatively, College of
Engineering computers have MATLAB already installed.
2) Download the function provided with the midterm and open it with MATLAB.
3) From the command window (main window that appears when you first open MATLAB),
you can run the function by typing the command
"[E, Vec, x, r, dx] = Schrod(V, L, N, eigenvector, width, omega, pot_depth, Z, l);"
with specific text values for V ('V_isw' for the infinite square well potential; 'V_fsw3' for
the finite square well potential; 'V_qho' for the quantum harmonic oscillator; 'V_H' for
the hydrogen atom) and numerical values for the rest.
Make sure the MATLAB path and the folder containing Schrod are one and the same by
navigating to the proper folder.
To see details about each of the function inputs, type “help Schrod” into the command
line.
The function will plot the wavefunction and output variables E, Vec, x, and r.

Problem 2: The Lennard-Jones Potential

Binding between pairs of inert-gas atoms can be modeled by the Lennard-Jones potential.
𝑟𝑟𝑚𝑚 12 𝑟𝑟𝑚𝑚 6
𝑉𝑉𝐿𝐿𝐿𝐿 = 𝜀𝜀 �� � − 2 � � �
𝑟𝑟 𝑟𝑟
At 𝑟𝑟𝑚𝑚 , the function reaches a minimum value −𝜀𝜀.

1. If we were to model this potential by a harmonic oscillator, what would be the

appropriate values of k and ω, in terms of 𝜀𝜀, 𝑟𝑟𝑚𝑚 , and the mass 𝑚𝑚?

2
 2. For argon, the values of 𝜀𝜀 = 10.35 meV and 𝑟𝑟𝑚𝑚 = 3.82 Å. Assume the mass of the
𝑚𝑚
system is the reduced mass 𝜇𝜇 = 2𝐴𝐴𝐴𝐴. Plot the ground-state wavef unction for the
Lennard-Jones potential and the ground state wave function for the harmonic oscillator
approximation on the same plot. Is the harmonic oscillator a good approximation of this
potential?
3. What is the zero-point energy of this system in each case?
4. At which eigenstate do the energies differ significantly? Can you explain this by
comparing the wavefunctions?

Problem 3: Bound States in an Asymmetric Well

∞, 𝑥𝑥 < 0
Consider a particle in one dimensional potential defined as 𝑉𝑉(𝑥𝑥) = �−𝑉𝑉0 , 0 < 𝑥𝑥 < 𝑎𝑎
0, 𝑎𝑎 < 𝑥𝑥

Answer the following questions:

a) Are bound states expected in the limits 𝑉𝑉0 → 0 and/or 𝑉𝑉0 → ∞?
Briefly explain your answer.
b) Provide general solutions for the wave function in Regions II (0 < 𝑥𝑥 < 𝑎𝑎) and III (𝑥𝑥 > 𝑎𝑎).
c) If there are one or more bound states, derive a single equation for the eigenvalues.
d) Derive the conditions for 𝑉𝑉0 under which solutions are possible in this case. Use a graph if
necessary.
e) For what values of 𝑉𝑉0 will there be multiple bound states in the well?

Note: this problem needs to be solved analytically, not numerically

Problem 4: Radial wave functions in the hydrogen atom

The third paragraph on p. 115 (starting with “We show in Fig. 3.2-2…”) contains a
mistake. What is the mistake? How should it be corrected?

3
Problem 5: Uncertainty Product for a Sinusoidal Wave Function

(σp is the standard deviation)

Problem 6: Commutators

Evaluate the commutators: (a) [(1/x), px], (b) [(1/x), px2], [x py – y px, y pz – z py]

How does the evaluation in part (c) relate to angular momentum?

Problem 7: Constructing a Hermitian Operator