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Statistical Physics of Particles

Mehran Kardar

Chapter 6

Quantum statistical mechanics - all with Video Answers

Educators


Chapter Questions

09:17

Problem 1

1. One-dimensional chair: a chain of $N+1$ particles of mass $m$ is connected by $N$ massless springs of spring constant $K$ and relaxed length $a$. The first and last particles are held fixed at the equilibrium separation of $N a$. Let us denote the longitudinal displacements of the particles from their equilibrium positions by $\left\{u_i\right\}$, with $u_0=u_N=0$ since the end particles are fixed. The Hamiltonian governing $\left\{u_i\right\}$, and the conjugate momenta $\left\{p_i\right\}$, is
$$
\mathcal{H}=\sum_{i=1}^{N-1} \frac{p_i^2}{2 m}+\frac{K}{2}\left[u_1^2+\sum_{i=1}^{N-2}\left(u_{i+1}-u_i\right)^2+u_{N-1}^2\right]
$$
(a) Using the appropriate (sine) Fourier transforms, find the normal modes $\left\{\tilde{u}_k\right\}$, and the corresponding frequencies $\left\{\omega_k\right\}$.
(b) Express the Hamiltonian in terms of the amplitudes of normal modes $\left\{\tilde{u}_k\right\}$, and evaluate the classical partition function. (You may integrate the $\left\{u_i\right\}$ from $-\infty$ to $+\infty$.
(c) First evaluate $\left\langle\left|\tilde{u}_k\right|^2\right\rangle$, and use the result to calculate $\left\{u_i^2 \mid\right.$. Plot the resulting squared displacement of each particle as a function of its equilibrium position.
(d) How are the results modified if only the first particle is fixed $\left(u_0=0\right)$, while the other end is free $\left(u_N \neq 0\right)$ ? (Note that this is a much simpler problem as the partition function can be evaluated by changing variables to the $N-1$ spring extensions.)

Robert Zaballa
Robert Zaballa
Numerade Educator
02:18

Problem 2

Black-hole thermodynamics: according to Bekenstein and Hawking, the entropy of a black hole is proportional to its area $A$, and given by
$$
S=\frac{k_B c^3}{4 G \hbar} A .
$$
(a) Calculate the escape velocity at a radius $R$ from a mass $M$ using classical mechanics. Find the relationship between the radius and mass of a black hole by setting this escape velocity to the speed of light $c$. (Relativistic calculations do not modify this result, which was originally obtained by Laplace.)
(b) Does entropy increase or decrease when two black holes collapse into one? What is the entropy change for the Universe (in equivalent number of bits of information) when two solar mass black holes $\left(M_{\odot} \approx 2 \times 10^{30} \mathrm{~kg}\right)$ coalesce?
(c) The internal energy of the black hole is given by the Einstein relation, $E=M c^2$. Find the temperature of the black hole in terms of its mass.
(d) A "black hole" actually emits thermal radiation due to pair creation processes on its event horizon. Find the rate of energy loss due to such radiation.
(e) Find the amount of time it takes an isolated black hole to evaporate. How long is this time for a black hole of solar mass?
(f) What is the mass of a black hole that is in thermal equilibrium with the current cosmic background radiation at $T=2.7 \mathrm{~K}$ ?
(g) Consider a spherical volume of space of radius $R$. According to the recently formulated Holographic Principle there is a maximum to the amount of entropy that this volume of space can have, independent of its contents! What is this maximal entropy?

Manish Jain
Manish Jain
Numerade Educator

Problem 3

Quantum harmonic oscillator: consider a single harmonic oscillator with the Hamiltonian
$$
\mathcal{H}=\frac{p^2}{2 m}+\frac{m \omega^2 q^2}{2}, \quad \text { with } \quad p=\frac{\hbar}{\mathrm{i}} \frac{\mathrm{d}}{\mathrm{d} q}
$$
(a) Find the partition function $Z$, at a temperature $T$, and calculate the energy $\langle\mathcal{H}\rangle$.
(b) Write down the formal expression for the canonical density matrix $\rho$ in terms of the eigenstates $\left(\{|n\rangle\}\right.$, and energy levels $\left(\left\{\epsilon_n\right\}\right)$ of $\mathcal{H}$.
(c) Show that for a general operator $A(x)$,
$$
\frac{\partial}{\partial x} \exp [A(x)] \neq \frac{\partial A}{\partial x} \exp [A(x)], \quad \text { unless } \quad\left[A, \frac{\partial A}{\partial x}\right]=0,
$$
while in all cases
$$
\frac{\partial}{\partial x} \operatorname{tr}\{\exp [A(x)]\}=\operatorname{tr}\left\{\frac{\partial A}{\partial x} \exp [A(x)]\right\}
$$
(d) Note that the partition function calculated in part (a) does not depend on the mass $m$, that is, $\partial Z / \partial m=0$. Use this information, along with the result in part (c), to show that
$$
\left\langle\frac{p^2}{2 m}\right\rangle=\left\langle\frac{m \omega^2 q^2}{2}\right\rangle .
$$
(e) Using the results in parts (d) and (a), or otherwise, calculate $\left\langle q^2\right\rangle$. How are the results in Problem 1 modified at low temperatures by inclusion of quantum mechanical effects?
(f) In a coordinate representation, calculate $\left\langle q^{\prime}|\rho| q\right\rangle$ in the high-temperature limit. One approach is to use the result
$$
\exp (\beta A) \exp (\beta B)=\exp \left[\beta(A+B)+\beta^2[A, B] / 2+\mathcal{O}\left(\beta^3\right)\right]
$$
(g) At low temperatures, $\rho$ is dominated by low-energy states. Use the ground state wave function to evaluate the limiting behavior of $\left\langle q^{\prime}|\rho| q\right\rangle$ as $T \rightarrow 0$.
(h) Calculate the exact expression for $\left\langle q^{\prime}|\rho| q\right\rangle$.

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Problem 4

Relativistic Coulomb gas: consider a quantum system of $N$ positive, and $N$ negative charged relativistic particles in a box of volume $V=L^3$. The Hamiltonian is
$$
\mathcal{H}=\sum_{i=1}^{2 N} c\left|\vec{p}_i\right|+\sum_{i<j}^{2 N} \frac{e_i e_j}{\left|\vec{r}_i-\vec{r}_j\right|}
$$
where $e_i=+e_0$ for $i=1, \cdots, N$, and $e_i=-e_0$ for $i=N+1, \cdots, 2 N$, denote the charges of the particles; $\left\{\vec{r}_i\right\}$ and $\left\{\vec{p}_i\right\}$ their coordinates and momenta, respectively. While this is too complicated a system to solve, we can nonetheless obtain some exact results.
(a) Write down the Schrödinger equation for the eigenvalues $\varepsilon_n(L)$, and (in coordinate space) eigenfunctions $\Psi_n\left(\left\{\vec{r}_i\right\}\right)$. State the constraints imposed on $\Psi_n\left(\left\{\vec{r}_i\right\}\right)$ if the particles are bosons or fermions.
(b) By a change of scale $\vec{r}_i^{\prime}=\vec{r}_i / L$, show that the eigenvalues satisfy a scaling relation $\varepsilon_n(L)=\varepsilon_n(1) / L$
(c) Using the formal expression for the partition function $Z(N, V, T)$, in terms of the eigenvalues $\left\{\varepsilon_n(L)\right\}$, show that $Z$ does not depend on $T$ and $V$ separately, but only on a specific scaling combination of them.
(d) Relate the energy $E$, and pressure $P$ of the gas to variations of the partition function. Prove the exact result $E=3 P V$.
(e) The Coulomb interaction between charges in $d$-dimensional space falls off with separation as $e_i e_j /\left|\vec{r}_i-\vec{r}_j\right|^{d-2}$. (In $d=2$ there is a logarithmic interaction.) In what dimension $d$ can you construct an exact relation between $E$ and $P$ for non-relativistic particles (kinetic energy $\sum_i \vec{p}_i^2 / 2 m$ )? What is the corresponding exact relation between energy and pressure?
(f) Why are the above "exact" scaling laws not expected to hold in dense (liquid or solid) Coulomb mixtures?

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Problem 5

The virial theorem is a consequence of the invariance of the phase space for a system of $N$ (classical or quantum) particles under canonical transformations, such as a change of scale. In the following, consider $N$ particles with coordinates $\left\{\vec{q}_i\right\}$, and conjugate momenta $\left\{\vec{p}_i\right\}$ (with $\left.i=1, \cdots, N\right)$, and subject to a Hamiltonian $\mathcal{H}\left(\left\{\vec{p}_i\right\},\left\{\vec{q}_i\right\}\right)$.
(a) Classical version: write down the expression for the classical partition function, $Z \equiv Z[\mathcal{H}]$. Show that it is invariant under the rescaling $\vec{q}_1 \rightarrow \lambda \vec{q}_1, \vec{p}_1 \rightarrow \vec{p}_1 / \lambda$ of a pair of conjugate variables, that is, $Z\left[\mathcal{H}_\lambda\right]$ is independent of $\lambda$, where $\mathcal{H}_\lambda$ is the Hamiltonian obtained after the above rescaling.
(b) Quantum mechanical version: write down the expression for the quantum partition function. Show that it is also invariant under the rescalings $\vec{q}_1 \rightarrow \lambda \vec{q}_1, \vec{p}_1 \rightarrow \vec{p}_1 / \lambda$, where $\vec{p}_i$ and $\vec{q}_i$ are now quantum mechanical operators. (Hint. Start with the timeindependent Schrödinger equation.)
(c) Now assume a Hamiltonian of the form
$$
\mathcal{H}=\sum_i \frac{\vec{p}_i^2}{2 m}+V\left(\left\{\vec{q}_i\right\}\right) .
$$
Use the result that $Z\left[\mathcal{H}_\lambda\right]$ is independent of $\lambda$ to prove the virial relation
$$
\left\langle\frac{\vec{p}_1^2}{m}\right\rangle=\left\langle\frac{\partial V}{\partial \vec{q}_1} \cdot \vec{q}_1\right\rangle
$$
where the brackets denote thermal averages.
(d) The above relation is sometimes used to estimate the mass of distant galaxies. The stars on the outer boundary of the G- 8.333 galaxy have been measured to move with velocity $v \approx 200 \mathrm{~km} \mathrm{~s}^{-1}$. Give a numerical estimate of the ratio of the G-8.333's mass to its size.

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08:06

Problem 6

Electron spin: the Hamiltonian for an electron in a magnetic field $\vec{B}$ is
$\mathcal{H}=-\mu_B \vec{\sigma} \cdot \vec{B}, \quad$ where $\quad \sigma_x=\left(\begin{array}{ll}0 & 1 \\ 1 & 0\end{array}\right), \quad \sigma_y=\left(\begin{array}{cc}0 & -\mathrm{i} \\ \mathrm{i} & 0\end{array}\right), \quad$ and $\quad \sigma_z=\left(\begin{array}{cc}1 & 0 \\ 0 & -1\end{array}\right)$ are the Pauli spin operators, and $\mu_B$ is the Bohr magneton.
(a) In the quantum canonical ensemble evaluate the density matrix if $\vec{B}$ is along the $z$ direction.
(b) Repeat the calculation assuming that $\vec{B}$ points along the $x$ direction.
(c) Calculate the average energy in each of the above cases.

Khoobchandra Agrawal
Khoobchandra Agrawal
Numerade Educator
00:26

Problem 7

Quantum rotor: consider a rotor in two dimensions with
$$
\mathcal{H}=-\frac{\hbar^2}{2 I} \frac{\mathrm{d}^2}{\mathrm{~d} \theta^2}, \quad \text { and } \quad 0 \leq \theta<2 \pi .
$$
(a) Find the eigenstates and energy levels of the system.
(b) Write the expression for the density matrix $\left\langle\theta^{\prime}|\rho| \theta\right\rangle$ in a canonical ensemble of temperature $T$, and evaluate its low- and high-temperature limits.

Stanley Enemuo
Stanley Enemuo
Numerade Educator

Problem 8

Quantum mechanical entropy: a quantum mechanical system (defined by a Hamiltonian $\mathcal{H}$ ), at temperature $T$, is described by a density matrix $\rho(t)$, which has an associated entropy $S(t)=-\operatorname{tr} \rho(t) \ln \rho(t)$
(a) Write down the time evolution equation for the density matrix, and calculate $\mathrm{d} S / \mathrm{d} t$.
(b) Using the method of Lagrange multipliers, find the density operator $\rho_{\max }$ that maximizes the functional $S[\rho]$, subject to the constraint of fixed average energy $\langle\mathcal{H}\rangle=$ $\operatorname{tr} \rho \mathcal{H}=E$
(c) Show that the solution to part (b) is stationary, that is, $\partial \rho_{\max } / \partial t=0$.

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01:03

Problem 9

Ortho/para-hydrogen: hydrogen molecules can exist in ortho and para states.
(a) The two electrons of $\mathrm{H}_2$ in para-hydrogen form a singlet (antisymmetric) state. The orbital angular momentum can thus only take even values; that is,
$$
\mathcal{H}_p=\frac{\hbar^2}{2 I} \ell(\ell+1),
$$
where $\ell=0,2,4, \cdots$. Calculate the rotational partition function of para-hydrogen, and evaluate its low- and high-temperature limits.
(b) In ortho-hydrogen the electrons are in a triply degenerate symmetric state, hence
$$
\mathcal{H}_o=\frac{\hbar^2}{2 I} \ell(\ell+1),
$$
with $\ell=1,3,5, \cdots$. Calculate the rotational partition function of ortho-hydrogen, and evaluate its low- and high-temperature limits.
(c) For an equilibrium gas of $N$ hydrogen molecules calculate the partition function. (Hint. Sum over contributions from mixtures of $N_p$ para- and $N_o=N-N_p$ orthohydrogen particles. Ignore vibrational degrees of freedom.)
(d) Write down the expression for the rotational contribution to the internal energy $\left\langle E_{\text {roL. }}\right\rangle$, and comment on its low- and high-temperature limits.
Actually, due to small transition rates between ortho- and para-hydrogen, in most circumstances the mixture is not in equilibrium.

Mayukh Banik
Mayukh Banik
Numerade Educator

Problem 10

Van Leeuwen's theorem: Consider a gas of charged particles subject to a general Hamiltonian of the form
$$
\mathcal{H}=\sum_{i=1}^N \frac{\vec{p}_i^2}{2 m}+U\left(\vec{q}_1, \cdots, \vec{q}_N\right) .
$$
In an external magnetic field, $\vec{B}$, the canonical momenta, $\vec{p}_n$, are replaced with $\vec{p}_n-e \vec{A}$, where $\vec{A}$ is the vector potential, $\vec{B}=\vec{\nabla} \times \vec{A}$. Show that if quantum effects are ignored, the thermodynamics of the problem is independent of $\vec{B}$.

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