For a degenerate Fermi gas, the Pauli exclusion principle restricts thermally changed occupations to an energy shell of width around the Fermi energy. The number of active Electrons is of order ; each carries an excitation energy of order . Thus the thermal energy grows as and the electronic heat capacity is proportional to .
More precisely, the fixed-particle-number Sommerfeld expansion givesHere is the total spin-summed density of states for the sample. For a three-dimensional parabolic band, , yieldingThe linear law concerns the electronic contribution; the low-temperature lattice heat capacity usually adds a term.
Let and be the carrier density and electronic heat capacity per unit volume. In isotropic kinetic theory, the angular average gives the electronic thermal conductivitywhere is the mean free path associated with the heat-current relaxation time. With ,The Drude model gives the electrical conductivity , where is the momentum relaxation time. ThereforeWhen the same approximately elastic collisions relax heat and charge currents, . Using gives the Wiedemann-Franz law is the Lorenz number. Degenerate electrons move at the Fermi velocity, not the classical thermal velocity; using classical equipartition would give the wrong coefficient.
The Wiedemann-Franz law applies to a normal degenerate metal when the same itinerant Electrons carry heat and charge, scattering is approximately elastic over the thermal shell, and the transport probability varies slowly across the energy interval around the Fermi level. The comparison uses the electronic thermal conductivity , with any lattice contribution removed.
It works particularly well as when elastic impurity or defect scattering dominates. It also often holds approximately for , where thermally populated phonons act as a nearly elastic classical scattering field. Room temperature need not lie above the Debye temperature for every metal.
At intermediate temperatures, inelastic small-angle electron-phonon scattering can relax heat much more efficiently than charge. Then and can be smaller than . Strong energy dependence of scattering, additional neutral heat carriers, or a transition out of the normal metallic state also invalidates the simple derivation. An observed deviation alone does not identify which assumption failed.
For one conduction electron per atom, let be the atom density. State counting in a Bloch band gives the Fermi wavevector . The Debye model preserves the three vibrational modes per atom by a spherical Debye wavevector cutoff , soBoth wavevectors are of order the inverse atomic spacing. The numerical factor uses the spherical Debye approximation; a real zone boundary and the largest-frequency mode depend on direction and branch. Because , short-wavelength acoustic phonons can scatter Fermi surface electrons through substantial angles. For nearly elastic scattering within a spherical Fermi surface,Near room temperature, when a substantial fraction of the phonon spectrum is occupied, electron-phonon scattering is often the main source of electrical resistance. For , the phonon population and scattering rate are approximately proportional to , giving , and roughly constant when the Wiedemann-Franz law holds.
For small-angle electron-phonon transport at low temperature, thermally active acoustic modes instead haveThey predominantly scatter forward. The factor makes such collisions inefficient at relaxing an electrical current, while a phonon energy of order can still substantially change an electron's thermal excitation. Heat-current relaxation therefore need not share the charge-current relaxation time. In the clean three-dimensional acoustic-phonon model this gives but , so the phonon-limited electrical resistivity scales as and . These laws describe the regime before residual elastic scattering takes over; at sufficiently low temperature impurities give nearly constant residual resistivity and , restoring the usual Lorenz number.[ref]
https://home.itp.ac.ru/~grigorev/LectureSlides/MetalsLecture2.pdf. Electron-phonon scattering: distinct low-temperature thermal and electrical transport relaxation rates
Phonons also transport heat themselves, with . At low temperature their population decreases and their phonon mean free path can become boundary- or defect-limited. At higher temperature Umklapp scattering can relax the phonon heat current. Such lattice conduction is an additional contribution, not the quantity constrained by the electronic Wiedemann-Franz law.
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