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Problem Set

Calculate the Fermi energy and Fermi temperature for sodium. Given: electron density n≈2.65×1028 m−3n \approx 2.65 \times 10^{28}\,\mathrm{m}^{-3}, me=9.109×10−31m_e = 9.109 \times 10^{-31} kg.

Solution

\varepsilon_F = \frac{\hbar^2}{2m_e}(3\pi^2 n)^{2/3}

= \frac{(1.055 \times 10^{-34})^2}{2 \times 9.109 \times 10^{-31}}(3\pi^2 \times 2.65 \times 10^{28})^{2/3}

(3π2×2.65×1028)1/3=(7.85×1029)1/3≈9.23×109(3\pi^2 \times 2.65 \times 10^{28})^{1/3} = (7.85 \times 10^{29})^{1/3} \approx 9.23 \times 10^9

(3π2n)2/3=(9.23×109)2=8.52×1019(3\pi^2 n)^{2/3} = (9.23 \times 10^9)^2 = 8.52 \times 10^{19}

εF=1.113×10−681.822×10−30×8.52×1019≈5.20×10−19 J≈3.25 eV\varepsilon_F = \frac{1.113 \times 10^{-68}}{1.822 \times 10^{-30}} \times 8.52 \times 10^{19} \approx 5.20 \times 10^{-19}\,\mathrm{J} \approx 3.25\,\mathrm{eV}

TF=εF/kB=5.20×10−19/1.381×10−23≈37700 KT_F = \varepsilon_F/k_B = 5.20 \times 10^{-19}/1.381 \times 10^{-23} \approx 37700\,\mathrm{K}

A 3D Bose gas of NN particles of mass mm is confined to volume VV. Show that the heat capacity at constant volume has a discontinuity at T=TcT = T_c and find the jump.

Solution

Above TcT_c (classical regime): CV=32NkBC_V = \frac{3}{2}Nk_B.

Below TcT_c: CV=154NkB ζ(5/2)/ζ(3/2)⋅(T/Tc)3/2C_V = \frac{15}{4}Nk_B\,\zeta(5/2)/\zeta(3/2) \cdot (T/T_c)^{3/2}.

At T=Tc−T = T_c^-:

C_V(T_c^-) = \frac{15}{4}Nk_B \cdot \frac{\zeta(5/2)}{\zeta(3/2)}

ζ(5/2)≈1.341\zeta(5/2) \approx 1.341, ζ(3/2)≈2.612\zeta(3/2) \approx 2.612:

C_V(T_c^-) = \frac{15}{4} \times \frac{1.341}{2.612},Nk_B \approx 1.926,Nk_B

At T=Tc+T = T_c^+: CV=32NkB=1.5 NkBC_V = \frac{3}{2}Nk_B = 1.5\,Nk_B.

The jump is ΔCV=CV(Tc−)−CV(Tc+)≈0.426 NkB\Delta C_V = C_V(T_c^-) - C_V(T_c^+) \approx 0.426\,Nk_B.

Derive the virial expansion for a non-ideal gas in terms of the second virial coefficient B2(T)B_2(T) And show that B2(T)B_2(T) can be expressed in terms of the two-particle interaction potential V(r)V(r).

Solution

The pressure of a real gas is expanded as PV/(NkBT)=1+B2(T) (N/V)+B3(T) (N/V)2+⋯PV/(Nk_BT) = 1 + B_2(T)\,(N/V) + B_3(T)\,(N/V)^2 + \cdots.

For a classical gas with pairwise interaction V(r12)V(r_{12}):

B_2(T) = -\frac{1}{2V}\int d^3\mathbf{r}_1,d^3\mathbf{r}2,\left[e^{-\beta V(r{12})} - 1\right]

= -2\pi \int_0^\infty \left[e^{-\beta V(r)} - 1\right] r^2, dr

For a hard-sphere gas (V(r)=∞V(r) = \infty for r<dr < d, V(r)=0V(r) = 0 for r>dr > d):

B_2 = -2\pi\int_0^d (-1),r^2,dr = \frac{2\pi d^3}{3} = \frac{2\pi}{3}\left(\frac{d}{2}\right)^3 \cdot 8 = 4v_0

Where v0=πd3/6v_0 = \pi d^3/6 is the volume of one sphere. The van der Waals excluded volume parameter is b=4Nv0=NB2b = 4Nv_0 = N B_2.

Show that the classical limit of the Fermi-Dirac distribution reproduces the Maxwell-Boltzmann distribution, and derive the condition for the classical limit in terms of the density of states.

Solution

The Fermi-Dirac distribution is:

f_{\mathrm{FD}(\varepsilon) = \frac{1}{e^{\beta(\varepsilon - \mu)} + 1}}

The total number of particles is:

N = \int_0^\infty \frac{g(\varepsilon)}{e^{\beta(\varepsilon - \mu)} + 1}, d\varepsilon

In the classical limit eβ(ε−μ)≫1e^{\beta(\varepsilon - \mu)} \gg 1 The +1+1 is negligible:

N \approx \int_0^\infty g(\varepsilon), e^{-\beta(\varepsilon - \mu)}, d\varepsilon = e^{\beta\mu} \int_0^\infty g(\varepsilon), e^{-\beta\varepsilon}, d\varepsilon

e^{\beta\mu} = \frac{N}{\int_0^\infty g(\varepsilon), e^{-\beta\varepsilon}, d\varepsilon} = \frac{N\lambda_{\mathrm{th}^3}{V}}

The classical limit requires eβμ≪1e^{\beta\mu} \ll 1 I.e., Nλth3/V≪1N\lambda_{\mathrm{th}^3/V \ll 1} Or equivalently, the average inter-particle spacing (V/N)1/3(V/N)^{1/3} must be much larger than λth\lambda_{\mathrm{th}}.

Compute the partition function for a single quantum harmonic oscillator and verify that the average energy is ⟨E⟩=ℏω(nB+1/2)\langle E \rangle = \hbar\omega(n_B + 1/2) where nB=1/(eβℏω−1)n_B = 1/(e^{\beta\hbar\omega} - 1).

Solution

Z_{\mathrm{HO} = \sum_{n=0}^{\infty} e^{-\beta\hbar\omega(n+1/2)} = e^{-\beta\hbar\omega/2}\sum_{n=0}^{\infty}\left(e^{-\beta\hbar\omega}\right)^n = \frac{e^{-\beta\hbar\omega/2}}{1 - e^{-\beta\hbar\omega}}}

\langle E \rangle = -\frac{\partial \ln Z}{\partial \beta} = \frac{\hbar\omega}{2} + \frac{\hbar\omega,e^{-\beta\hbar\omega}}{1 - e^{-\beta\hbar\omega}} = \frac{\hbar\omega}{2} + \frac{\hbar\omega}{e^{\beta\hbar\omega} - 1} = \hbar\omega\left(\frac{1}{2} + n_B\right)

At high TT (β→0\beta \to 0): ⟨E⟩→kBT\langle E \rangle \to k_BT (equipartition). At low TT: ⟨E⟩→ℏω/2\langle E \rangle \to \hbar\omega/2 (zero-point energy).

A paramagnetic salt consists of NN non-interacting spin-1/2 particles with magnetic moment μ\mu. The system is placed in an external magnetic field BB at temperature TT. Compute the magnetisation MM and the magnetic susceptibility χ=(∂M/∂B)T\chi = (\partial M/\partial B)_T.

Solution

For a single spin-1/2 particle, the energy levels are E↑=−μBE_\uparrow = -\mu B and E↓=+μBE_\downarrow = +\mu B. The single-particle partition function is:

Z_1 = e^{\beta\mu B} + e^{-\beta\mu B} = 2\cosh(\beta\mu B)

For NN non-interacting spins, Z=Z1N=[2cosh⁡(βμB)]NZ = Z_1^N = [2\cosh(\beta\mu B)]^N.

The magnetisation is:

M = \frac{1}{\beta}\frac{\partial \ln Z}{\partial B} = N\mu\tanh(\beta\mu B)

The susceptibility at small BB (or high TT, where βμB≪1\beta\mu B \ll 1):

\chi = N\mu^2\beta,\mathrm{sech}^2(\beta\mu B) \approx \frac{N\mu^2}{k_B T}

This is the Curie law χ=C/T\chi = C/T with C=Nμ2/kBC = N\mu^2/k_B, showing that paramagnetic susceptibility obeys a 1/T1/T dependence at high temperatures. ■\blacksquare

Derive the Stefan-Boltzmann law for blackbody radiation from the Planck distribution. Compute the photon number density and the average energy per photon at temperature TT.

Solution

The Planck distribution gives the spectral energy density:

u(\omega, T) = \frac{\hbar\omega^3}{\pi^2 c^3}\frac{1}{e^{\beta\hbar\omega} - 1}

Integrating over all frequencies:

U(T) = \int_0^\infty u(\omega, T),d\omega = \frac{\hbar}{\pi^2 c^3}\int_0^\infty \frac{\omega^3}{e^{\beta\hbar\omega} - 1},d\omega

Let x=βℏωx = \beta\hbar\omega:

U(T)=(kBT)4π2c3ℏ3∫0∞x3ex−1 dx=π2kB415c3ℏ3T4=σT4U(T) = \frac{(k_B T)^4}{\pi^2 c^3 \hbar^3}\int_0^\infty \frac{x^3}{e^x - 1}\,dx = \frac{\pi^2 k_B^4}{15 c^3 \hbar^3} T^4 = \sigma T^4

where σ=π2kB4/(60ℏ3c2)\sigma = \pi^2 k_B^4/(60\hbar^3 c^2) is the Stefan-Boltzmann constant.

The photon number density is:

n = \int_0^\infty \frac{\omega^2}{\pi^2 c^3}\frac{1}{e^{\beta\hbar\omega} - 1}\,d\omega = \frac{2\zeta(3)}{\pi^2}\left(\frac{k_B T}{\hbar c}\right)^3 The average energy per photon is $\langle E \rangle = U/n = (\pi^4/30\zeta(3))k_B T \approx 2.701\,k_B T$. $\blacksquare$ </details> ### Problem 8 For the Ising model on a 2D square lattice, explain why the mean-field approximation predicts a phase transition at $T_c = zJ/k_B$ (where $z = 4$ for the square lattice), while the exact Onsager solution gives $T_c \approx 2.269 J/k_B$. Why is mean-field theory inaccurate in low dimensions? <details> <summary>Solution</summary> In mean-field theory, each spin experiences an effective field $B_{\text{eff}} = zJ\langle s \rangle$. The self-consistency equation is $\langle s \rangle = \tanh(\beta z J \langle s \rangle)$. For $T > T_c^{\text{MF}} = zJ/k_B$, only the trivial solution $\langle s \rangle = 0$ exists; below $T_c^{\text{MF}}$, a non-zero magnetisation appears. For the square lattice, $z = 4$, so $T_c^{\text{MF}} = 4J/k_B$. The exact Onsager solution gives $T_c \approx 2.269 J/k_B$. The discrepancy arises because mean-field theory neglects fluctuations, which are significant in low dimensions. In 1D, mean-field theory incorrectly predicts a phase transition at finite $T$, while the exact solution shows no spontaneous magnetisation at any $T > 0$. The lower critical dimension for the Ising model is $d = 1$, below which fluctuations destroy long-range order. $\blacksquare$ </details> ### Problem 9 A system consists of $N$ distinguishable three-level particles, each with energies $0$, $\varepsilon$, and $2\varepsilon$. The system is in contact with a heat bath at temperature $T$. (a) Write the single-particle partition function. (b) Find the average energy of the system. (c) Compute the heat capacity $C_V$ and sketch it as a function of $T$. What is the limiting behaviour as $T \to 0$ and $T \to \infty$? <details> <summary>Solution</summary> (a) $Z_1 = 1 + e^{-\beta\varepsilon} + e^{-2\beta\varepsilon}$. (b) For $N$ distinguishable particles, $Z = Z_1^N$. The average energy is: $$\langle E \rangle = -\frac{\partial \ln Z}{\partial \beta} = -N\frac{\partial \ln Z_1}{\partial \beta} = N\frac{\varepsilon e^{-\beta\varepsilon} + 2\varepsilon e^{-2\beta\varepsilon}}{1 + e^{-\beta\varepsilon} + e^{-2\beta\varepsilon}} (c) $C_V = \frac{\partial \langle E \rangle}{\partial T} = \frac{1}{k_B T^2}\frac{\partial \langle E \rangle}{\partial \beta}$. As $T \to 0$: $\beta \to \infty$, all particles are in the ground state, $\langle E \rangle \to 0$, $C_V \to 0$ (all degrees of freedom frozen out). As $T \to \infty$: $\beta \to 0$, all three states are equally populated with probability $1/3$, $\langle E \rangle \to N\varepsilon$, $C_V \to 0$ (saturation). The heat capacity shows a peak (Schottky anomaly) at intermediate temperatures where the thermal energy $k_B T$ is comparable to $\varepsilon$. $\blacksquare$ </details> ## Intuition Thermal physics connects the microscopic world of individual particles to the macroscopic world of temperature, pressure, and entropy. The partition function is the central object: it encodes all thermodynamic information about a system by summing Boltzmann weights over every possible state. From it, one can derive free energies, equations of state, and response functions. The key insight is that entropy counts the number of microstates consistent with a macrostate, and equilibrium corresponds to the macrostate with the most microstates. ## Cross-References - **[Statistical Mechanics](/2-thermal-physics/2_statistical-mechanics/)**: The Fermi energy and partition function calculations in this problem set apply the canonical ensemble methods from this chapter. - **[Fermi Gas at Finite Temperature](/2-thermal-physics/4_fermi-gas-at-finite-temperature/)**: The Fermi energy problems are direct applications of the finite-temperature electron gas theory. - **[Classical Limit and the Maxwell-Boltzmann Distribution](/2-thermal-physics/7_classical-limit-and-the-maxwell-boltzmann-distribution/)**: The high-temperature limit of quantum statistics recovers the classical ideal gas results tested in several problems. - [Calculus](https://mathematics.wyattau.com/docs/calculus) - [Linear Algebra](https://mathematics.wyattau.com/2-linear-algebra/) - [Vector Calculus](https://mathematics.wyattau.com/docs/vector-calculus) - [Quantum Computing](https://computer-science.wyattau.com/docs/quantum-computing) ## Common Mistakes **Using wrong units for temperature in statistical mechanics:** All statistical formulas require absolute temperature (Kelvin). Using Celsius or Fahrenheit gives exponentially wrong Boltzmann factors. **Confusing specific heat at constant volume vs pressure:** C_V = (∂U/∂T)_V; C_P = (∂H/∂T)_P. For ideal gases C_P = C_V + nR, but this relation fails for real gases and solids. **Forgetting the density of states in Fermi energy calculations:** The Fermi energy depends on the number density n through E_F = (ℏ²/2m)(3π²n)^(2/3). Omitting the density of states factor gives incorrect degeneracy temperatures. ## Related in this track - [Bose-Einstein Condensation](/2-thermal-physics/5_bose-einstein-condensation/) - [Classical Limit and the Maxwell-Boltzmann Distribution](/2-thermal-physics/7_classical-limit-and-the-maxwell-boltzmann-distribution/) - [Common Pitfalls](/2-thermal-physics/8_common-pitfalls/) - [Fermi Gas at Finite Temperature](/2-thermal-physics/4_fermi-gas-at-finite-temperature/)