In a metal, a partially filled energy band or overlapping energy bands supplies Electrons with nearby unoccupied states. At thermal equilibrium, oppositely directed group velocities are equally populated and the net electric current vanishes. An applied electric field distorts the occupation distribution, producing a small mean drift velocity. A filled energy band alone has no such low-field intraband response because its velocity contributions cancel over the entire Brillouin zone.
In the Drude model, let be the mobile Electron number density, let be the elementary charge, and let be the momentum relaxation time. The mean motion obeys
The steady state is . The current density is opposite to the Electron drift velocity:
This gives microscopic Ohm's law, with electrical conductivity in and electrical resistivity in . For a uniform wire of length and cross-sectional area , its electrical resistance is . The dissipated power per volume is , the Joule heating supplied by the external source.
The free electron model with Fermi-Dirac statistics improves the microscopic picture. The Pauli exclusion principle fills states up to the Fermi energy at low temperature. For a spherical, parabolic energy band with two spin states,
Only states near the Fermi surface change their occupation in a weak-field response; the large equilibrium Fermi velocity is not the small drift velocity. The same formula results for this isotropic parabolic model when is evaluated for transport near the Fermi surface. In a crystal, the energy band group velocity, effective mass and possibly direction-dependent scattering replace the simplest bare-particle picture. The mean free path is approximately .
A perfectly periodic static lattice is already included in Bloch states and does not by itself give a finite electrical resistivity. Momentum relaxation comes from defects, impurities, boundaries, and electron-phonon scattering. Independent scattering mechanisms approximately add their rates, giving Matthiessen's rule,
The approximately temperature-independent is the residual resistivity. In ordinary simple metals, the phonon contribution is approximately proportional to temperature at high temperature; a three-dimensional acoustic-phonon transport model gives a contribution well below the relevant Debye temperature. Other mechanisms can dominate in particular materials or regimes, so neither power law is universal.
The classical Drude model incorrectly treats the equilibrium carrier statistics. Fermi-Dirac statistics explains the small electronic heat capacity, while electrons carrying both charge and heat give the approximate Wiedemann-Franz law for degenerate carriers with appropriate nearly elastic scattering. Both the simple electrical conductivity formula and this thermal relation depend on the assumptions about energy bands and scattering, rather than being exact for all metals.
The Debye model approximates a three-dimensional crystal as an elastic continuum supporting quantized normal modes, or phonons. At long wavelengths, the acoustic phonon branches have approximately linear dispersion relations : one longitudinal branch and two transverse branches. Replace their complicated actual spectra by these linear forms, then introduce a cutoff chosen to preserve the total vibrational degrees of freedom for atoms. This is an approximation to the spectrum, not a claim that a real crystal has no non-acoustic branches.
For periodic boundary conditions in volume , each allowed wavevector occupies in the space of wavevectors. Counting a spherical shell for each branch gives the density of states per unit angular frequency
An effective speed of sound can be defined by . In the single-speed Debye model, choose so that
Thus the Debye wavevector, Debye frequency and Debye temperature satisfy
Here has units of seconds when angular frequency is measured in ; its integral is the dimensionless number of normal modes. The spherical cutoff replaces the real Brillouin zone by an equal-count continuum construction.
Each phonon mode is a quantum harmonic oscillator. Since phonon number is not conserved at thermal equilibrium, the chemical potential is zero and its Bose-Einstein distribution gives mean thermal energy . The zero-point energy is independent of temperature in the harmonic, fixed-volume approximation and does not contribute to the heat capacity at constant volume. Excluding that constant term,
Differentiating the first integral at fixed volume avoids losing the temperature-dependent upper limit in the second one. The resulting Debye heat capacity is
For , extend the upper limit to infinity. Expanding and integrating term by term gives . Therefore
This law follows from the three-dimensional density of states and the availability only of low-frequency modes at low temperature. It is a central success of the Debye model.
For , the Bose-Einstein distribution reduces to the classical equipartition theorem: every mode contributes thermal energy . Consequently
the Dulong-Petit law, or per mole of atoms. The simple model omits detailed phonon dispersion relation, distinct optical phonon branches, and anharmonic effects such as thermal expansion. In a metal, the low-temperature total heat capacity additionally contains a term approximately proportional to from Electrons, so the lattice term should not be mistaken for the whole measurement.

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