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Quantum Statistics in Detail

15.1 Fermi—Dirac and Bose—Einstein Distributions

Section titled “15.1 Fermi—Dirac and Bose—Einstein Distributions”

For non-interacting quantum particles:

ni=1eβ(ϵiμ)±1\langle n_i \rangle = \frac{1}{e^{\beta(\epsilon_i - \mu)} \pm 1}

Where ++ is for fermions (Fermi—Dirac) and - for bosons (Bose—Einstein).

Fermions (half-integer spin): Pauli exclusion limits ni1\langle n_i \rangle \leq 1.

Bosons (integer spin): No restriction on occupation number; ni\langle n_i \rangle can diverge when ϵi=μ\epsilon_i = \mu.

For a 3D gas of NN non-interacting fermions in volume VV:

N=k1eβ(2k2/2mμ)+1continuumV(2π)3d3kf(ϵk)N = \sum_{\mathbf{k}} \frac{1}{e^{\beta(\hbar^2 k^2/2m - \mu)} + 1} \xrightarrow{\text{continuum} \frac{V}{(2\pi)^3}\int d^3k\, f(\epsilon_k)}

The Fermi energy at T=0T = 0:

ϵF=22m(3π2n)2/3\epsilon_F = \frac{\hbar^2}{2m}(3\pi^2 n)^{2/3}

Where n=N/Vn = N/V is the number density. The Fermi temperature is TF=ϵF/kBT_F = \epsilon_F/k_B.

At low temperature (TTFT \ll T_F), the Sommerfeld expansion gives:

E=35NϵF[1+5π212(TTF)2+]E = \frac{3}{5}N\epsilon_F\left[1 + \frac{5\pi^2}{12}\left(\frac{T}{T_F}\right)^2 + \cdots\right]

CV=NkBπ22TTF+C_V = Nk_B\frac{\pi^2}{2}\frac{T}{T_F} + \cdots

The linear specific heat is a hallmark of degenerate Fermi systems.

15.3 The Bose Gas and Bose—Einstein Condensation

Section titled “15.3 The Bose Gas and Bose—Einstein Condensation”

For bosons, the chemical potential must satisfy μϵ0\mu \leq \epsilon_0 (ground state energy). When μϵ0\mu \to \epsilon_0A macroscopic fraction of particles condenses into the ground state.

The critical temperature for BEC in 3D:

Tc=2π2mkB(nζ(3/2))2/3T_c = \frac{2\pi\hbar^2}{mk_B}\left(\frac{n}{\zeta(3/2)}\right)^{2/3}

Where ζ(3/2)2.612\zeta(3/2) \approx 2.612.

Below TcT_cThe condensate fraction is:

N0N=1(TTc)3/2\frac{N_0}{N} = 1 - \left(\frac{T}{T_c}\right)^{3/2}

Worked Example 15.1: Fermi Energy of Copper

Copper has one conduction electron per atom, atomic mass 63.563.5 g/mol, density 8.968.96 g/cm3^3.

n=8.96×103 kg/m363.5×103 kg/mol×NA=1.41×1029 m3×6.022×1023=8.49×1028 m3n = \frac{8.96 \times 10^3 \text{ kg/m}^3}{63.5 \times 10^{-3} \text{ kg/mol} \times N_A = 1.41 \times 10^{29} \text{ m}^{-3} \times 6.022 \times 10^{23} = 8.49 \times 10^{28} \text{ m}^{-3}}

ϵF=22me(3π2×8.49×1028)2/3\epsilon_F = \frac{\hbar^2}{2m_e}(3\pi^2 \times 8.49 \times 10^{28})^{2/3}

=(1.055×1034)22×9.109×1031×(2.52×1030)2/3= \frac{(1.055 \times 10^{-34})^2}{2 \times 9.109 \times 10^{-31}} \times (2.52 \times 10^{30})^{2/3}

=1.113×10681.822×1030×1.846×1020= \frac{1.113 \times 10^{-68}}{1.822 \times 10^{-30}} \times 1.846 \times 10^{20}

=6.11×1039×1.846×1020=1.13×1018 J= 6.11 \times 10^{-39} \times 1.846 \times 10^{20} = 1.13 \times 10^{-18} \text{ J}

TF=1.13×10181.38×102381900 KT_F = \frac{1.13 \times 10^{-18}}{1.38 \times 10^{-23}} \approx 81\,900 \text{ K}

This is enormously higher than room temperature, confirming that conduction electrons in metals form a highly degenerate Fermi gas.

Worked Example 15.2: BEC in a Trap

For N=106N = 10^6 rubidium-87 atoms in a harmonic trap with frequency ωˉ/(2π)=100\bar{\omega}/(2\pi) = 100 Hz:

In a harmonic trap, the density of states is g(ϵ)=ϵ2/(23ωˉ3)g(\epsilon) = \epsilon^2/(2\hbar^3\bar{\omega}^3)Giving:

Tc=ωˉkB(6Nπ2ζ(3))1/3T_c = \frac{\hbar\bar{\omega}}{k_B}\left(\frac{6N}{\pi^2\zeta(3)}\right)^{1/3}

=1.055×1034×2π×1001.38×1023(6×106π2×1.202)1/3= \frac{1.055 \times 10^{-34} \times 2\pi \times 100}{1.38 \times 10^{-23}}\left(\frac{6 \times 10^6}{\pi^2 \times 1.202}\right)^{1/3}

=6.63×10321.38×1023×(5.07×105)1/3= \frac{6.63 \times 10^{-32}}{1.38 \times 10^{-23}} \times (5.07 \times 10^5)^{1/3}

=4.81×109×79.7383 nK= 4.81 \times 10^{-9} \times 79.7 \approx 383 \text{ nK}

This is consistent with the 1995 Cornell—Wieman BEC experiment.

ConceptRelationSignificance
Distribution functionni=(eβ(ϵiμ)±1)1\langle n_i \rangle = (e^{\beta(\epsilon_i-\mu)} \pm 1)^{-1}Unified form for FD/BE
Fermi energyϵF=2(3π2n)2/3/(2m)\epsilon_F = \hbar^2(3\pi^2 n)^{2/3}/(2m)Sets scale for degenerate fermions
BEC critical temperatureTc=2π2n2/3/(mkBζ(3/2)2/3)T_c = 2\pi\hbar^2 n^{2/3}/(mk_B \zeta(3/2)^{2/3})Phase transition temperature
Sommerfeld expansionCVT/TFC_V \propto T/T_FLinear specific heat at low TT
Condensate fractionN0/N=1(T/Tc)3/2N_0/N = 1 - (T/T_c)^{3/2}Order parameter for BEC
  1. Confusing FD and BE limits: At high temperature (TTFT \gg T_F or TTcT \gg T_c), both distributions reduce to the Maxwell—Boltzmann distribution. The quantum statistical corrections vanish when the interparticle spacing is much larger than the thermal de Broglie wavelength.

  2. Chemical potential for bosons: For bosons, μ\mu must always be less than the ground state energy. Setting μ>ϵ0\mu > \epsilon_0 gives negative occupation numbers, which is unphysical. At TcT_c, μ0\mu \to 0 (for a free gas with ϵ0=0\epsilon_0 = 0).

  3. Continuum approximation validity: The g(ϵ)ϵg(\epsilon) \propto \sqrt{\epsilon} density of states assumes a large volume. For small systems (nanoparticles, quantum dots), the discrete level structure becomes important and the integral approximation fails.

  4. BEC requires dimensionality: In 1D and 2D, Bose—Einstein condensation does not occur in a uniform gas (Hohenberg’s theorem). Trapping potentials can, however, create quasi-condensates in lower dimensions.

  • Metals and degenerate fermions: The electron specific heat CV=γTC_V = \gamma T in metals directly reflects the Fermi degeneracy. The Sommerfeld parameter γ\gamma measures the density of states at the Fermi level.
  • Ultracold atoms: BEC in dilute atomic gases (Rb, Na, Li) enables studies of superfluidity, quantised vortices, and matter-wave interferometry.
  • Neutron stars: Degenerate neutron Fermi pressure supports neutron stars against gravitational collapse, with ϵF50\epsilon_F \sim 50 MeV.
  • White dwarfs: Electron degeneracy pressure balances gravity, with the Chandrasekhar mass limit arising from relativistic Fermi gas physics.
  • Particle physics: Neutrinos in the early universe follow FD statistics. The neutrino background temperature (Tν1.95T_\nu \approx 1.95 K) is slightly lower than the CMB due to e+ee^+e^- annihilation heating the photon bath.
  • Condensed matter: Heavy fermion materials have effective masses mmem^* \gg m_e, producing Fermi temperatures TF10T_F \sim 10100100 K where quantum degeneracy meets accessible laboratory conditions.
  • Cosmology: The Bose—Einstein condensate has been proposed as a dark matter candidate (fuzzy dark matter), with a de Broglie wavelength of kiloparsec scales smoothing small-scale structure.
  • Quantum information: Degenerate Fermi gases in optical lattices simulate the Hubbard model, with the Pauli exclusion principle naturally enforcing the no-double-occupancy constraint at half-filling.

Summary Table: Comparison of Quantum and Classical Gases

Section titled “Summary Table: Comparison of Quantum and Classical Gases”
PropertyMaxwell—BoltzmannFermi—DiracBose—Einstein
ParticlesDistinguishableIndistinguishable fermionsIndistinguishable bosons
Occupationni=e(ϵiμ)/kBT\langle n_i \rangle = e^{-(\epsilon_i-\mu)/k_BT}ni1\langle n_i \rangle \leq 1ni\langle n_i \rangle unrestricted
Low-TT behaviourAll in ground stateFermi seaBEC
CVC_V at low TT32NkB\frac{3}{2}Nk_BT\propto TT3/2\propto T^{3/2}
Validity conditionnλth31n\lambda_{\text{th}}^3 \ll 1nλth31n\lambda_{\text{th}}^3 \gtrsim 1nλth32.612n\lambda_{\text{th}}^3 \gtrsim 2.612
Symmetry of wavefunctionNo constraintAntisymmetricSymmetric