These notes from week 6 of https://paradigms.oregonstate.edu/courses/ph441 cover the ideal gas from a grand canonical standpoint starting with the solutions to a particle in a three-dimensional box. They include a number of small group activities.

Treat the ground state of a quantum particle-in-a-box as a periodic function.

1. Set up the integrals for the Fourier series for this state.

2. Which terms will have the largest coefficients? Explain briefly.

3. Are there any coefficients that you know will be zero? Explain briefly.

4. Using the technology of your choice or by hand, calculate the four largest coefficients. With screen shots or otherwise, show your work.

5. Using the technology of your choice, plot the ground state and your approximation on the same axes.

You know that the normalized spatial eigenfunctions for a particle in a 1-D box of length \(L\) are \(\sqrt{\frac{2}{L}}\sin{\frac{n\pi x}{L}}\). If you want the eigenfunctions for a particle in a 2-D box, then you just multiply together the eigenfunctions for a 1-D box in each direction. (This is what the separation of variables procedure tells you to do.)

1. Find the normalized eigenfunctions for a particle in a 2-D box with sides of length \(L\) in the \(x\)-direction and length \(W\) in the \(y\)-direction.
2. Find the Hamiltonian for a 2-D box and show that your eigenstates are indeed eigenstates and find a formula for the possible energies

3. Any sufficiently smooth spatial wave function inside a 2-D box can be expanded in a double sum of the product wave functions, i.e. \begin{equation} \psi(x,y)=\sum_{n=1}^{\infty}\sum_{m=1}^{\infty}\, c_{nm}\; \hbox{eigenfunction}_n(x)\;\hbox{eigenfunction}_m(y) \end{equation} Using your expressions from part (a) above, write out all the terms in this sum out to \(n=3\), \(m=3\). Arrange the terms, conventionally, in terms of increasing energy.

   You may find it easier to work in bra/ket notation: \begin{align*} \left|{\psi}\right\rangle &=\sum_{n=1}^{\infty}\sum_{m=1}^{\infty}\, c_{nm}\left|{n}\right\rangle \left|{m}\right\rangle \\ &=\sum_{n=1}^{\infty}\sum_{m=1}^{\infty}\, c_{nm}\left|{nm}\right\rangle \end{align*}

4. Find a formula for the \(c_{nm}\)s in part (c). Find the formula first in bra ket notation and then rewrite it in wave function notation.

Students implement a finite-difference approximation for the kinetic energy operator as a matrix, and then use numpy to solve for eigenvalues and eigenstates, which they visualize.

Students find matrix elements of the position operator \(\hat x\) in a sinusoidal basis. This allows them to express this operator as a matrix, which they can then numerically diagonalize and visualize the eigenfunctions.

Students compute inner products to expand a wave function in a sinusoidal basis set. This activity introduces the inner product for wave functions, and the idea of approximating a wave function using a finite set of basis functions.

Students use a PhET simulation to explore the time evolution of a particle in an infinite square well potential.

Students compute probabilities and averages given a probability density in one dimension. This activity serves as a soft introduction to the particle in a box, introducing all the concepts that are needed.

Students solve for the equations of motion of a box sliding down (frictionlessly) a wedge, which itself slides on a horizontal surface, in order to answer the question "how much time does it take for the box to slide a distance \(d\) down the wedge?". This activities highlights finding kinetic energies when the coordinate system is not orthonormal and checking special cases, functional behavior, and dimensions.

As discussed in class, we can consider a black body as a large box with a small hole in it. If we treat the large box a metal cube with side length \(L\) and metal walls, the frequency of each normal mode will be given by: \begin{align} \omega_{n_xn_yn_z} &= \frac{\pi c}{L}\sqrt{n_x^2 + n_y^2 + n_z^2} \end{align} where each of \(n_x\), \(n_y\), and \(n_z\) will have positive integer values. This simply comes from the fact that a half wavelength must fit in the box. There is an additional quantum number for polarization, which has two possible values, but does not affect the frequency. Note that in this problem I'm using different boundary conditions from what I use in class. It is worth learning to work with either set of quantum numbers. Each normal mode is a harmonic oscillator, with energy eigenstates \(E_n = n\hbar\omega\) where we will not include the zero-point energy \(\frac12\hbar\omega\), since that energy cannot be extracted from the box. (See the Casimir effect for an example where the zero point energy of photon modes does have an effect.)

Note

This is a slight approximation, as the boundary conditions for light are a bit more complicated. However, for large \(n\) values this gives the correct result.

1. Show that the free energy is given by \begin{align} F &= 8\pi \frac{V(kT)^4}{h^3c^3} \int_0^\infty \ln\left(1-e^{-\xi}\right)\xi^2d\xi \\ &= -\frac{8\pi^5}{45} \frac{V(kT)^4}{h^3c^3} \\ &= -\frac{\pi^2}{45} \frac{V(kT)^4}{\hbar^3c^3} \end{align} provided the box is big enough that \(\frac{\hbar c}{LkT}\ll 1\). Note that you may end up with a slightly different dimensionless integral that numerically evaluates to the same result, which would be fine. I also do not expect you to solve this definite integral analytically, a numerical confirmation is fine. However, you must manipulate your integral until it is dimensionless and has all the dimensionful quantities removed from it!

2. Show that the entropy of this box full of photons at temperature \(T\) is \begin{align} S &= \frac{32\pi^5}{45} k V \left(\frac{kT}{hc}\right)^3 \\ &= \frac{4\pi^2}{45} k V \left(\frac{kT}{\hbar c}\right)^3 \end{align}

3. Show that the internal energy of this box full of photons at temperature \(T\) is \begin{align} \frac{U}{V} &= \frac{8\pi^5}{15}\frac{(kT)^4}{h^3c^3} \\ &= \frac{\pi^2}{15}\frac{(kT)^4}{\hbar^3c^3} \end{align}

Students see probability density for eigenstates and linear combinations of eigenstates for a particle on a ring. The three visual representations: standard position vs probability density plot, a ring with colormapping, and cylindrical plot with height and colormapping, are also animated to visualize time-evolution.

Students calculate probabilities for a particle on a ring using three different notations: Dirac bra-ket, matrix, and wave function. After calculating the angular momentum and energy measurement probabilities, students compare their calculation methods for notation.

Students calculate probabilities for energy, angular momentum, and position as a function of time for an initial state that is a linear combination of energy/angular momentum eigenstates for a particle confined to a ring written in bra-ket notation. This activity helps students build an understanding of when they can expect a quantity to depend on time and to give them more practice moving between representations.

Students calculate probabilities for a particle on a ring whose wavefunction is not easily separated into eigenstates by inspection. To find the energy, angular momentum, and position probabilities, students perform integrations with the wavefunction or decompose the wavefunction into a superposition of eigenfunctions.

Students calculate the expectation value of energy and angular momentum as a function of time for an initial state for a particle on a ring. This state is a linear combination of energy/angular momentum eigenstates written in bra-ket notation.

Students use their arms to act out stationary and non-stationary states of a quantum particle on a ring.

Students explore the effects of putting a point charge at various places inside, outside, and on the surface of a cubical Gaussian surface. The Mathematica worksheet or Sage activity shows the electric field due to the charge, then plots the the flux integrand on the top surface of the box, calculates the flux through the top of the box, and the value of the flux through the whole cube.

• Students need to understand that the surface represents the electric potential in the center of a parallel plate capacitor. Try doing the activity Electric Potential of Two Charged Plates before this activity.
• Students should know that
  1. objects with like charge repel and opposite charge attract,
  2. object tend to move toward lower energy configurations
  3. The potential energy of a charged particle is related to its charge: \(U=qV\)
  4. The force on a charged particle is related to its charge: \(\vec{F}=q\vec{E}\)

• Divergence of a vector field (at a point) is the flux per unit volume through an infinitesimal box.
• How to predict the sign and relative magnitude of the divergence from graphs of a vector field.
• (Optional) How to calculate the divergence of a vector field with computer algebra.