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Problem Set

Calculate the Fermi energy and Fermi temperature for sodium. Given: electron density n2.65×1028m3n \approx 2.65 \times 10^{28}\,\mathrm{m}^{-3}, me=9.109×1031m_e = 9.109 \times 10^{-31} kg.

Solution

εF=22me(3π2n)2/3\varepsilon_F = \frac{\hbar^2}{2m_e}(3\pi^2 n)^{2/3}

=(1.055×1034)22×9.109×1031(3π2×2.65×1028)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)1/39.23×109(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=1.113×10681.822×1030×8.52×10195.20×1019J3.25eV\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=5.20×1019/1.381×102337700KT_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=154NkBζ(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=TcT = T_c^-:

CV(Tc)=154NkBζ(5/2)ζ(3/2)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:

CV(Tc)=154×1.3412.612NkB1.926NkBC_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=1.5NkBC_V = \frac{3}{2}Nk_B = 1.5\,Nk_B.

The jump is ΔCV=CV(Tc)CV(Tc+)0.426NkB\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}):

B2(T)=12Vd3r1d3r2[eβV(r12)1]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]

=2π0[eβV(r)1]r2dr= -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):

B2=2π0d(1)r2dr=2πd33=2π3(d2)38=4v0B_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:

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

The total number of particles is:

N=0g(ε)eβ(εμ)+1dεN = \int_0^\infty \frac{g(\varepsilon)}{e^{\beta(\varepsilon - \mu)} + 1}\, d\varepsilon

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

N0g(ε)eβ(εμ)dε=eβμ0g(ε)eβεdεN \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 eβμ1e^{\beta\mu} \ll 1I.e., Nλth3/V1N\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=ω(nB+1/2)\langle E \rangle = \hbar\omega(n_B + 1/2) where nB=1/(eβω1)n_B = 1/(e^{\beta\hbar\omega} - 1).

Solution

ZHO=n=0eβω(n+1/2)=eβω/2n=0(eβω)n=eβω/21eβωZ_{\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}}}

E=lnZβ=ω2+ωeβω1eβω=ω2+ωeβω1=ω(12+nB)\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 (β0\beta \to 0): EkBT\langle E \rangle \to k_BT (equipartition). At low TT: Eω/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:

Z1=eβμB+eβμB=2cosh(βμB)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=1βlnZB=Nμtanh(βμB)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 βμB1\beta\mu B \ll 1):

χ=Nμ2βsech2(βμB)Nμ2kBT\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(ω,T)=ω3π2c31eβω1u(\omega, T) = \frac{\hbar\omega^3}{\pi^2 c^3}\frac{1}{e^{\beta\hbar\omega} - 1}

Integrating over all frequencies:

U(T)=0u(ω,T)dω=π2c30ω3eβω1dωU(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=βωx = \beta\hbar\omega:

U(T)=(kBT)4π2c330x3ex1dx=π2kB415c33T4=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/(603c2)\sigma = \pi^2 k_B^4/(60\hbar^3 c^2) is the Stefan-Boltzmann constant.

The photon number density is:

n=0ω2π2c31eβω1dω=2ζ(3)π2(kBTc)3n = \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 E=U/n=(π4/30ζ(3))kBT2.701kBT\langle E \rangle = U/n = (\pi^4/30\zeta(3))k_B T \approx 2.701\,k_B T.

\blacksquare

For the Ising model on a 2D square lattice, explain why the mean-field approximation predicts a phase transition at Tc=zJ/kBT_c = zJ/k_B (where z=4z = 4 for the square lattice), while the exact Onsager solution gives Tc2.269J/kBT_c \approx 2.269 J/k_B. Why is mean-field theory inaccurate in low dimensions?

Solution

In mean-field theory, each spin experiences an effective field Beff=zJsB_{\text{eff}} = zJ\langle s \rangle. The self-consistency equation is s=tanh(βzJs)\langle s \rangle = \tanh(\beta z J \langle s \rangle). For T>TcMF=zJ/kBT > T_c^{\text{MF}} = zJ/k_B, only the trivial solution s=0\langle s \rangle = 0 exists; below TcMFT_c^{\text{MF}}, a non-zero magnetisation appears.

For the square lattice, z=4z = 4, so TcMF=4J/kBT_c^{\text{MF}} = 4J/k_B. The exact Onsager solution gives Tc2.269J/kBT_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 TT, while the exact solution shows no spontaneous magnetisation at any T>0T > 0. The lower critical dimension for the Ising model is d=1d = 1, below which fluctuations destroy long-range order. \blacksquare

A system consists of NN distinguishable three-level particles, each with energies 00, ε\varepsilon, and 2ε2\varepsilon. The system is in contact with a heat bath at temperature TT. (a) Write the single-particle partition function. (b) Find the average energy of the system. (c) Compute the heat capacity CVC_V and sketch it as a function of TT. What is the limiting behaviour as T0T \to 0 and TT \to \infty?

Solution

(a) Z1=1+eβε+e2βεZ_1 = 1 + e^{-\beta\varepsilon} + e^{-2\beta\varepsilon}.

(b) For NN distinguishable particles, Z=Z1NZ = Z_1^N. The average energy is:

= 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>