The Debye model treats a solid's low-frequency lattice vibrations as acoustic phonons in an elastic continuum. There are three polarizations per wavevector, one longitudinal and two transverse, with approximately linear dispersion relations. A cutoff is chosen to preserve the total vibrational modes of atoms. The phonon number itself is not fixed; mode occupations follow the Bose-Einstein distribution with zero chemical potential.
For one polarization of speed , counting wavevector states in a spherical shell gives . Define an average Debye speed by . The total density of states can then be written
The Debye wavevector is , the Debye frequency is , and the Debye temperature is .
Omitting the temperature-independent zero-point energy, the vibrational energy and resulting Debye heat capacity are
At low temperature the upper limit can be extended to infinity. The integral is , giving
Only the long-wavelength acoustic modes are appreciably populated, explaining the Debye T-cubed test. At high temperature every mode contributes by equipartition theorem, so , the Dulong-Petit law.
The model succeeds especially at low temperature, where long-wavelength elasticity is reliable. It replaces real anisotropic branches by a simple continuum and cannot reproduce detailed optical phonon branches or every intermediate-temperature feature. Metals also have an electronic heat capacity approximately proportional to ; defects, magnetic excitations or a phase transition can add other terms. Experiments often measure heat capacity at constant pressure, which need not equal the harmonic model's exactly.
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.
In the three-dimensional Debye model, the lattice has normal modes for atoms. Replacing their dispersion by a linear acoustic dispersion up to a cutoff gives the Debye heat capacity
At low temperature the upper limit can be replaced by infinity. Since the integral then equals ,
At high temperature each harmonic mode contributes by the equipartition theorem, giving the Dulong-Petit law
For one mole replace by . The curve starts with zero slope, rises as , and levels off toward the classical limit. This is the lattice contribution; a metal's electronic heat capacity is a separate low-temperature term.
The Debye wavevector follows by counting three polarizations inside the cutoff sphere:
With the supplied speed of sound treated as the effective Debye speed, and
Here . Real crystals have different longitudinal and transverse sound speeds; the one-speed estimate uses the stated value, rather than inferring those unprovided branches.
Figure 1.
Debye lattice heat capacity and the squared magnitude of the Drude conductivity
. Details.
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 , so
Both 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 have
They 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]
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.