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The Lorenz number is the ratio $L=K_e/(\sigma T)$. The Sommerfeld value $L_0=({\pi }^2/3)(k_B/e{)}^2\simeq 2.44\times 10^{-8}\mathrm{W}\mathrm{\Omega }{\mathrm{K}}^{-2}$ applies under the assumptions of the Wiedemann-Franz law. The ratio must use electronic thermal conductivity if lattice heat flow is appreciable.

At low carrier concentration, $|S|$ can be large but electrical conductivity is too small. Increasing the carrier concentration usually increases $\sigma =ne\mu$, while $|S|$ decreases. Electronic thermal conductivity rises approximately as ${\kappa }_e=L\sigma T$ by the Wiedemann-Franz law; lattice conduction supplies an additional background. Thus neither an insulator nor an ordinary metal usually maximizes $Z$.

Heavily doped semiconductors and semimetals often give the useful compromise, near a maximum of $S^2\sigma /\kappa$ as doping is varied. The optimum is material- and temperature-dependent; there is no universal optimal concentration.

For one homogeneous thermoelectric material, the dimensional thermoelectric figure of merit isThe dimensionless quantity is $ZT$. The Seebeck coefficient $S$ measures the open-circuit voltage response to a temperature difference and reflects the energy asymmetry of charge-carrier transport. The electrical conductivity $\sigma$ depends on carrier density and mobility and sets electrical loss; $\rho =1/\sigma$. The thermal conductivity is $\kappa ={\kappa }_e+{\kappa }_l$, with contributions from carriers and phonons, and represents unwanted heat leakage.

Increasing carrier concentration usually raises $\sigma$ while reducing $|S|$ once transport becomes strongly degenerate. The electronic part of $\kappa$ also tends to rise, approximately through the Wiedemann-Franz law where applicable. This competition produces an intermediate optimum, commonly in heavily doped semiconductors, rather than in a very resistive insulator or an ordinary high-carrier-density metal. The optimum depends on band structure and scattering; the schematic is not a universal measured concentration curve.

The material figure of merit isLarge thermoelectric power factor supplies electrical output, while low thermal conductivity limits heat leaking without useful conversion. For a constant-property ideal generator, a common approximation isIncreasing the appropriately averaged figure of merit raises efficiency toward, but not beyond, the Carnot limit. Actual devices also incur contact, geometric and heat-transfer losses, and a single peak material ZT does not specify their efficiency.

The supplied trends show the trade-off with carrier density: conductivity rises, the magnitude of the Seebeck coefficient tends to fall, and electronic thermal conductivity rises approximately with conductivity through the Wiedemann-Franz law. Thus neither arbitrarily high doping nor maximization of conductivity alone gives the best ZT; the power factor and thermal terms produce an intermediate optimum.

Two complementary strategies are:

Both strategies must be checked for mobility penalties and electronic heat transport. Simply suppressing every kind of transport would also suppress electrical output.

The Wiedemann-Franz law relates the electronic part of thermal conductivity to electrical conductivity:For degenerate electrons with elastic scattering and a transport function smooth over $k_{B}T$, a Sommerfeld expansion makes the same Fermi-level transport factor appear in charge conduction and in heat conduction. Their ratio cancels that factor and leaves the displayed Lorenz number. Heat conductivity is defined at zero electric current, so thermoelectric subtraction is part of the precise transport expression.

The law does not relate total solid heat conductivity to charge conductivity when phonons contribute substantially. Strong inelastic scattering, sharp energy dependence, nondegenerate carriers or nonstandard electronic regimes can change the ratio. Low-temperature residual elastic-scattering transport is a common setting where the standard value is recovered. The unit W·ohm/K² follows because ${\kappa }_e/(\sigma T)$ contains one extra inverse temperature beyond thermal conductivity itself.

The free electron model replaces the microscopic ionic potential and interacting electronic motion by independent mobile electrons in a uniform neutralizing background, with approximately parabolic dispersion $ϵ={\hslash }^2{k}^2/(2m^{\ast })$. Its quantum version fills states according to Fermi-Dirac statistics and the Pauli exclusion principle. Scattering is represented by a momentum relaxation time $\tau$, rather than derived from the model's ideal free trajectories. This model explains a Fermi energy much larger than room-temperature thermal energy, an electronic heat capacity proportional to temperature at low temperature, and a Drude electrical conductivity. With appropriate scattering assumptions it also yields the Wiedemann-Franz law. It cannot by itself explain band gaps, detailed band anisotropy, strong correlations, or the microscopic temperature dependence of $\tau$.

The inertial term is mass times the rate of change of mean drift velocity. The electric force is $eE$, taking the printed $e$ as the signed electron charge, and $-\gamma ⟨v⟩=-m^{\ast }⟨v⟩/\tau$ describes loss of directed momentum to scattering. electrons retain large microscopic velocities; this damping is of their mean directed motion. In a steady DC field,Both charge factors are negative for electrons, so the conductivity is positive. If $e$ instead denotes a positive charge magnitude, the force and current equations each require a minus sign and give the same result.

For AC response choose physical fields as real parts of phasors proportional to $e^{-i\omega t}$. Substitution givesThusThe real part decreases from ${\sigma }_0$ to zero. The imaginary part starts at zero, reaches ${\sigma }_0/2$ at $\omega \tau =1$, and falls as $1/\omega$. The real part falls as $1/{\omega }^2$ at high frequency. With an $e^{+i\omega t}$ convention, only the sign of the imaginary part changes. Positive $\mathrm{Re}\sigma$ gives positive cycle-averaged dissipation $⟨jE⟩=\mathrm{Re}\sigma |\hat{E}{|}^2/2$.

The supplied DC conductivity determines the transport time:Inertia matters when $\omega \tau \sim 1$, giving ${\omega }_c\simeq 4.02\times 10^{13}\mathrm{rad}{\mathrm{s}}^{-1}$, or ${\nu }_c={\omega }_c/(2\pi )\simeq 6.40\times 10^{12}\mathrm{Hz}$. Quoting the former number as hertz would introduce an erroneous factor of $2\pi$.

The free electron model replaces the detailed periodic potential by a constant background, treating conduction electrons as mobile particles with approximately parabolic dispersion $E={\hslash }^2{k}^2/(2m)$. It is useful to distinguish the classical Drude model from the quantum free electron gas. They share a simple transport picture, but differ fundamentally in occupation statistics.

With a momentum-relaxation time $\tau$, both lead in a simple isotropic one-band approximation toThis explains approximately Ohmic longitudinal conduction and a carrier-density scale from the Hall effect. The relaxation time is phenomenological: introducing it does not itself predict scattering from defects or phonons. A four-probe resistance measurement separates the sample's longitudinal response from current-contact voltage drops; field and current reversals isolate the transverse signal.

The classical model incorrectly assigns roughly $3N{k}_B/2$ of electronic heat capacity, far too large in a degenerate metal. Fermi-Dirac statistics fixes this: most occupied states cannot change occupation after a small thermal perturbation because nearby low-energy states are already filled. Only a fraction of order $k_{B}T/E_F$ near the Fermi energy participates. For $T\ll T_F$,The quantum model also gives a finite Fermi velocity even at zero temperature and Pauli paramagnetism. Under predominantly elastic scattering, its electronic heat and charge conductivities obey the Wiedemann-Franz law,This is a quantum success; classical equipartition does not give the correct small heat capacity and Lorenz number together.

Its limitations are equally instructive. Without the periodic potential it has no band gaps, so it cannot distinguish a filled-band insulator from a metal or explain semiconductor doping. The simplest single-electron Hall formula cannot explain positive Hall coefficients; band curvature and electron holes, or a multiband transport treatment, are needed. It neglects much Fermi-surface anisotropy and detailed optical interband absorption. Noninteracting electrons alone do not explain ferromagnetism or superconductivity, and lattice thermal behavior needs phonons. The nearly-free electron model, which allows reciprocal-lattice Fourier components of the potential to mix plane waves, provides a controlled first correction near Bragg planes.

Its main success is a simple quantitative baseline for degenerate conduction electrons; its main failure is treating the crystal and interactions as too featureless. A fit of conductivity alone is not a test of the whole model: compare heat capacity, Hall sign, optical response and temperature dependence using independently constrained parameters.

In a metal, mobile electrons transport heat as well as electric charge. A temperature gradient creates an imbalance between carriers arriving from warmer and colder regions. The resulting heat current obeys Fourier's law ${\mathbf{j}}_Q=-\kappa \nabla T$ for an isotropic material, where thermal conductivity $\kappa$ has units $\mathrm{W}{\mathrm{m}}^{-1}{\mathrm{K}}^{-1}$. For a bar of area $A$ carrying steady heat flow $P$, $P=-\kappa AdT/dx$ when parasitic losses are negligible.

A kinetic estimate for the electronic contribution iswhere $C_e$ is the electronic heat capacity per volume, $v_F$ the Fermi velocity, and ${\ell }_{\kappa }=v_F{\tau }_{\kappa }$ the heat-transport mean free path. Fermi-Dirac statistics and the Pauli exclusion principle restrict thermal rearrangements to states near the Fermi surface, rather than allowing every electron to contribute a classical heat capacity. A degenerate parabolic band givesUsing the Drude model form $\sigma =n{e}^2{\tau }_{\sigma }/m$ for electrical transport, the relation between thermal and electrical relaxation times in metals becomesFor scattering that relaxes heat and charge currents similarly, ${\tau }_{\kappa }\simeq {\tau }_{\sigma }$ and the Wiedemann-Franz law follows:Thus good electrical conductors are usually good thermal conductors. The correct quantum Lorenz number differs from a naive classical electron-gas estimate.

Scattering from impurities, boundaries and phonons limits the heat-transport path. In an impurity-dominated low-temperature regime with approximately constant relaxation time, ${\kappa }_e$ is approximately proportional to $T$. Where phonon-limited electrical resistivity is proportional to $T$ and the Wiedemann-Franz approximation is applicable, ${\kappa }_e$ can be roughly temperature independent. Inelastic processes can relax heat and charge currents differently, so the Lorenz ratio is not universal at all temperatures. Lattice phonons add a separate positive thermal contribution; the measured total is $\kappa ={\kappa }_e+{\kappa }_{\mathrm{ph}}$, and the electronic Wiedemann-Franz expression should not be applied blindly to that total.

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 $n$ be the mobile electron number density, let $e>0$ be the elementary charge, and let $\tau$ be the momentum relaxation time. The mean motion obeysThe steady state is ${\mathbf{v}}_d=-e\tau \mathbf{E}/m$. The current density is opposite to the electron drift velocity:This gives microscopic Ohm's law, with electrical conductivity $\sigma$ in $\mathrm{S}{\mathrm{m}}^{-1}$ and electrical resistivity ${\rho }_{\mathrm{el}}$ in $\Omega \mathrm{m}$. For a uniform wire of length $\ell$ and cross-sectional area $A$, its electrical resistance is $R={\rho }_{\mathrm{el}}\ell /A$. The dissipated power per volume is $\mathbf{J}\cdot \mathbf{E}=\sigma E^2$, 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 $n{e}^2\tau /m$ formula results for this isotropic parabolic model when $\tau$ 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 ${\ell }_{\mathrm{mfp}}=v_F\tau$.

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 ${\rho }_0$ 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 $T^5$ 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 ${\kappa }_e/(\sigma T)={\pi }^2{k}_B^2/(3e^2)$ 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.

Let $n=N/\mathcal{V}$ and $c_e=C_e/\mathcal{V}$ be the carrier density and electronic heat capacity per unit volume. In isotropic kinetic theory, the angular average $⟨v_x^2⟩=v_F^2/3$ gives the electronic thermal conductivitywhere ${\ell }_Q=v_F{\tau }_Q$ is the mean free path associated with the heat-current relaxation time. With $v_F^2=2E_F/m^{\ast }$,The Drude model gives the electrical conductivity $\sigma =n{e}^2{\tau }_{\sigma }/m^{\ast }$, where ${\tau }_{\sigma }$ is the momentum relaxation time. ThereforeWhen the same approximately elastic collisions relax heat and charge currents, ${\tau }_Q={\tau }_{\sigma }$. Using $A={\pi }^2/2$ gives the Wiedemann-Franz law$L_0$ 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 $k_{B}T$ around the Fermi level. The comparison uses the electronic thermal conductivity $K_e$, with any lattice contribution removed.

It works particularly well as $T\to 0$ when elastic impurity or defect scattering dominates. It also often holds approximately for ${\Theta }_D\ll T\ll T_F$, 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 ${\tau }_Q\ne {\tau }_{\sigma }$ and $K_e/(\sigma T)$ can be smaller than $L_0$. 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 $n_a$ be the atom density. State counting in a Bloch band gives the Fermi wavevector $k_F=(3{\pi }^2{n}_a{)}^{1/3}$. The Debye model preserves the three vibrational modes per atom by a spherical Debye wavevector cutoff $q_D=(6{\pi }^2{n}_a{)}^{1/3}$, 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 $q_D<2k_F$, 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 $T\gg {\Theta }_D$, the phonon population and scattering rate are approximately proportional to $T$, giving $\rho \propto T$, $\sigma \propto T^{-1}$ and roughly constant $K_e$ 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 $1-\cos \theta$ makes such collisions inefficient at relaxing an electrical current, while a phonon energy of order $k_{B}T$ 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 ${\tau }_Q^{-1}\propto T^3$ but ${\tau }_{\sigma }^{-1}\propto T^5$, so the phonon-limited electrical resistivity scales as $T^5$ and $K_e\propto T^{-2}$. These laws describe the regime before residual elastic scattering takes over; at sufficiently low temperature impurities give nearly constant residual resistivity and $K_e\propto T$, restoring the usual Lorenz number.^[ref]

Phonons also transport heat themselves, with $K_{\mathrm{ph}}\simeq c_{\mathrm{ph}}{c}_s{\ell }_{\mathrm{ph}}/3$. 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.

For a degenerate isotropic parabolic electron band, electrical conductivity is $\sigma =n{e}^2{\tau }_{\sigma }/m$ and electronic thermal conductivity is ${\kappa }_e={\pi }^{2}n{k}_B^{2}T{\tau }_{\kappa }/(3m)$. Their ratio is ${\kappa }_e/(\sigma T)=L_0{\tau }_{\kappa }/{\tau }_{\sigma }$, where $L_0=({\pi }^2/3)(k_B/e{)}^2$ is the Lorenz number. Nearly elastic scattering that relaxes charge and heat currents similarly gives ${\tau }_{\kappa }\simeq {\tau }_{\sigma }$ and the Wiedemann-Franz law. Inelastic scattering can relax heat current and directed momentum differently, invalidating the simplest identification even in a good metal.

The Wiedemann-Franz law relates the electronic thermal conductivity of a normal degenerate metal to its electrical conductivity:An isotropic kinetic theory estimate gives $K_e=c_e{v}_F^2{\tau }_Q/3$. With electronic heat capacity density $c_e={\pi }^{2}n{k}_B^{2}T/(2E_F)$, $v_F^2=2E_F/m^{\ast }$ and $\sigma =n{e}^2{\tau }_{\sigma }/m^{\ast }$, the ratio is $L_0{\tau }_Q/{\tau }_{\sigma }$. 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]