For a degenerate isotropic parabolic electron band, electrical conductivity is and electronic thermal conductivity is . Their ratio is , where is the Lorenz number. Nearly elastic scattering that relaxes charge and heat currents similarly gives and the Wiedemann-Franz law. Inelastic scattering can relax heat current and directed momentum differently, invalidating the simplest identification even in a good metal.
Thermionic emission 2026-10-18
Heating a metal gives some Electrons enough energy to escape its surface. A heated diode cathode can therefore supply an electric current across a vacuum gap to a collecting diode anode. This makes temperature a control for the supply of Electrons. Conversely, measuring that supply at several temperatures lets us estimate the surface work function: the energy barrier measured from the Fermi level to the nearby vacuum level. A Richardson plot turns the strong exponential function dependence into a slope.
Three questions must be kept separate: how many Electrons cross the surface, how many traverse the gap, and how many the collecting diode anode records. The Richardson-Dushman law answers the first under specified surface assumptions. Space charge can obstruct the second, while incomplete collection can alter the third.
Thermionic tail-flux derivation 2026-10-18
Consider a planar surface with outward normal along . For an auxiliary equilibrium electron gas just outside it, let be the total number density, counting both signs of . Its Maxwell-Boltzmann velocity distribution has normal-component densityAn Electron with crosses more area per unit time when it moves faster. The outgoing number flux therefore uses , rather than just the probability of :This integral contributes only . Holding a classical bulk number density fixed and imposing a normal kinetic energy threshold would instead give ; that argument alone does not produce .
For the ideal surface model, measure external Electron energies from the metal's chemical potential . A freely propagating external state has . When , its Fermi-Dirac distribution reduces to the Maxwell–Boltzmann statistics tail. Counting two spin states per phase space cell of volume givesEach of the three Gaussian integrals supplies . Combining this state count with the crossing factor givesThe auxiliary atmosphere supplies an equilibrium state-counting argument; an operating collector removes the outgoing Electrons. It need not maintain a real equilibrium gas throughout the gap. Unit transmission and the ideal free Electron state count are substantive assumptions, so this calculation does not determine an arbitrary real surface's measured .
In particular, Electrons inside a metal generally form a degenerate Fermi gas. A classical distribution for the escaping tail does not imply a classical distribution for the whole interior. Richardson himself emphasized this distinction in his lecture.[ref]
Thermionic Phenomena and the Laws which Govern Them by Owen Willans Richardson. Nobel Lectures, Physics 1922–1941; pp. 230–231, internal versus external electron statistics
Wiedemann-Franz law 2026-10-18
The Wiedemann-Franz law relates the electronic thermal conductivity of a normal degenerate metal to its electrical conductivity:An isotropic kinetic theory estimate gives . With electronic heat capacity density , and , the ratio is . Approximately elastic scattering with a smooth energy dependence gives equal heat and charge relaxation times. Inelastic electron-phonon scattering can make them different; the law also concerns the electronic contribution, not additional lattice heat conduction.[ref]
https://arxiv.org/abs/1810.05646. Abstract: acoustic-phonon violations at finite temperature and restoration when impurity scattering dominates