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.
A solid stores thermal energy in lattice vibrations and, when available, electronic and other excitations. For a nonmagnetic insulating crystal at sufficiently low temperature, the gap suppresses mobile electronic excitations and the leading bulk contribution normally comes from acoustic phonons. The three-dimensional Debye heat capacity is
The vibrational density of states scales as , so only a fraction proportional to of the modes is thermally active at low temperature. The two limiting forms are
The high-temperature value is the Dulong-Petit law, or per mole of atoms. Optical phonons add thermally activated contributions as their characteristic energies become accessible. A multiatom cell has more branches, but still three vibrational degrees of freedom per atom.
A normal metal has an additional low-temperature electronic heat capacity. The Pauli exclusion principle restricts excitations to a shell of width about around the Fermi energy. The number of thermally active Electrons is therefore proportional to , rather than the total Electron number contributing a classical heat capacity. With spin-summed electronic density of states for the whole specimen,
For a three-dimensional free-electron gas, and . Only a small fraction of the classical electronic value is accessible when , even though the electronic term dominates the phonon term as in a normal gapless metal.
Figure 1.
Debye lattice heat capacity and the low-temperature electronic intercept in a normal metal
. Details.
Plotting against gives a straight line with intercept and slope in the appropriate low-temperature range. This separates the electronic density-of-states information from the acoustic-phonon scale. In a Fermi liquid, the interacting quasiparticle density of states replaces the free value, so an enhanced effective mass enhances .
The qualifications matter experimentally. Superconductivity can gap electronic excitations, magnetic order adds magnetic excitations, defects can generate additional low-temperature terms, and low-dimensional or very small specimens need not obey the bulk cubic law. The Debye expression is for constant-volume heat capacity; constant-pressure heat capacity differs through thermal expansion, although the difference is often small at low temperature. Thus the normal-metal and ordinary insulating limits are useful leading behaviors, not universal formulas for every solid in every phase.
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.
A neutral two-dimensional linear electronic spectrum has heat capacity proportional to , while three-dimensional acoustic phonons have Debye heat capacity proportional to . Thus their ratio scales as . At fixed crystal composition and shape, for linear size , favoring the electronic surface contribution in smaller or colder specimens. The continuum laws require thermally populated wavelengths small compared with sample size; their formal low-temperature crossover need not lie inside that regime.