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The electric potential difference corresponding to thermal energy $k_{B}T$ per elementary charge $q$.

Release of electrons from a heated material; one source of electrons in an X-ray tube.

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.

The coefficient $A$ has dimensions of electric current density divided by squared temperature. For ideal nonrelativistic particles with the free electron mass, two spin states, a planar uniform surface, and unit escape transmission, the thermionic tail-flux derivation giveswhere $e$ is the positive elementary charge and $h$ is the Planck constant. The two area units differ by a factor of $10^4$. A fitted $A$ need not equal $A_0$: reflection at the surface, the electronic band structure, and uncertain emitting area affect the inferred coefficient. A constant escape transmission $\tau$ would give $A=\tau A_0$ in this simple model; an energy-dependent transmission generally requires an integral instead.

The name joins Owen Willans Richardson with Saul Dushman. Dushman's 1923 paper develops a thermodynamic treatment of electron emission analogous to evaporation and evaluates the prefactor using quantum ideas.^[ref]

A thermodynamic system is in thermodynamic equilibrium when its macroscopic state has no spontaneous tendency to change through any exchange allowed by its constraints. For an isolated system, stable thermodynamic equilibrium maximizes entropy over the accessible states at fixed total energy and conserved material inventories. A wall can forbid an exchange, so always specify what can cross or move. Thermal, mechanical and chemical conditions answer different questions about that same constrained state. ^[ref]

For example, two compartments separated by a rigid, impermeable wall that transmits heat can reach thermal equilibrium while retaining different pressures and compositions. Allowing an unloaded piston to move adds a mechanical equilibrium condition. Allowing one chemical species to cross adds chemical potential equality for particle exchange; allowing a chemical reaction adds its chemical equilibrium condition. A fixed barrier can therefore support a constrained thermodynamic equilibrium that ceases to be an equilibrium when the barrier is removed.

Uniformity is not the definition of thermodynamic equilibrium. An isothermal atmosphere in hydrostatic equilibrium can have a common temperature while its pressure and mass density vary with height: the pressure gradient balances gravity. In an external field, the exchange condition must include the relevant potential energy; for charged matter this leads to the electrochemical potential. Relativistic gravitational corrections to thermal equilibrium are described separately by the Tolman temperature law.

A steady state only says that the macroscopic description is constant in time. A bar maintained between hot and cold thermal reservoirs has steady heat flux and produces entropy, so it is not in thermodynamic equilibrium. Even matching temperatures at one perfect-contact interface can coexist with heat transfer through the surrounding material; matching those two local values does not establish equilibrium of the whole apparatus. See thermal conduction for that spatial transport problem.

The useful simplification is that equilibrium conditions predict an endpoint without computing every collision or flow during relaxation. The first law of thermodynamics supplies the conserved quantities, and the Second law of thermodynamics supplies the direction of change. For a system held at fixed temperature and volume, the corresponding criterion is minimization of Helmholtz free energy; at fixed temperature and pressure, it is minimization of Gibbs free energy, with the material and exchange constraints still imposed.

The thermodynamic limit describes a sequence of larger systems, not a single enormous specimen: particle number $N$ and volume $V$ tend to infinity with number density $n=N/V$ fixed. Hold the chosen intensive and extensive thermodynamic quantities such as temperature $T$ and an applied magnetic field fixed along that sequence. In the canonical ensemble the controls are $T,N,V$; in the grand canonical ensemble one instead fixes $T$ and chemical potential, and the limiting number density is a result, possibly with a jump at phase coexistence. These are different specifications of a limiting experiment.

The useful limit is usually an intensive and extensive thermodynamic quantities normalization of the Helmholtz free energy, not a finite limit of the total extensive quantity itself:Here $Z_{N,V}$ is the canonical partition function, $k_B$ is the Boltzmann constant, $f$ is free-energy density, and $a$ is Helmholtz free energy per particle. Thus $F_{N,V}=Vf+o(V)$ when the limit exists; finite systems need not be exactly extensive quantities because of the surface correction to thermodynamic free energy.

Specify the interactions and the growing containers too. For a conventional fluid, use a fixed stable pair potential with a tempered pair potential tail, and containers whose boundary layer of any fixed thickness occupies a vanishing fraction of the volume; uniformly enlarged cubes work, a tube of fixed cross-section does not give the same bulk limit. For a finite-range Ising model, keep the lattice spacing and bond coupling fixed while enlarging all intended spatial directions. Ordinary bounded wall interactions or periodic boundary conditions can then give the same bulk free-energy density, although boundary conditions can select different spontaneous symmetry breaking states. This is a set of hypotheses, not a theorem that every interaction has a boundary-independent limit.^[ref]

The Curie–Weiss model below deliberately uses a different limiting prescription: its all-to-all coupling is divided by $N$. Without that factor its interaction energy would grow as $N^2$, rather than as an extensive quantity. The model has no spatial wall or correlation length to compare with a container; it is an exactly summable illustration of finite-size rounding, not a quantitative model of the fluid experiment below.

Thermodynamics studies energy transfers and the constraints on macroscopic changes. Its vocabulary connects internal energy, entropy, temperature, pressure and volume to heat and work. The first law of thermodynamics balances energy; the Second law of thermodynamics decides which changes can occur spontaneously and limits how much work a heat engine can deliver. These principles let us bound performance before choosing a material or a detailed machine design. Applications include power generation, propulsion and refrigerators. ^[ref]

Start by choosing a system boundary. A closed system can exchange energy but no matter; an isolated system exchanges neither. A state function, such as internal energy or entropy, depends on the equilibrium state. A process specifies how that state changes. Thus a body's temperature is a property it has, whereas heat records energy crossing its boundary during a process. A body contains internal energy, rather than a stored quantity of heat.

Two insulated bodies initially at different positive temperatures approach thermal equilibrium when brought into thermal contact. Their combined energy is conserved, but their combined entropy increases. They do not spontaneously separate again into a hotter body and a colder one. This familiar asymmetry makes thermodynamics interesting: conserving energy leaves many imaginable changes available, and entropy supplies a further constraint. The same distinction underlies both entropy maximization under thermal contact and the thermal efficiency limit in Carnot's theorem.

A thermodynamic system is the part of the physical world selected for an energy and matter balance. Draw its boundary before classifying an interaction as heat, work or transported matter. The boundary may move: a sealed piston encloses a closed system even while its volume changes. An isolated system additionally excludes all external energy transfers.^[ref]

Boundary choice changes the ledger. If an electrical heater warms water, choosing only the water counts incoming heat; including the heater counts electrical work entering through its leads. The combined internal energy records storage, without separate stored categories for the two transfer mechanisms.^[ref]

The chosen steady-state model isHere $U$ is the terminal voltage drop along positive electric current through the module. Its Seebeck effect term opposes the cooling supply. The cold Peltier effect term removes heat; Joule heating and returning heat conduction reduce the available cooling. At zero electric current, $Q_c=Q_h=-K\Delta T$: the passive leak warms c and removes heat from h, consistent with the stated signs. Subtracting the two face equations cancels heat conduction and gives the electrical power, an independent conservation of energy check.

The factor one half is an ideal-model result, not a universal rule for every contact. To see its origin, let $x$ run from cold to hot along a uniform equivalent leg of length $L$, cross-sectional area $A$, electrical resistivity $\rho$ and thermal conductivity $\kappa$. With constant coefficients, insulated sides and no Thomson effect, steady conservation of energy givesThe Fourier's law heat current in the positive $x$ direction is $-\kappa A{T}^{\prime }$. At $x=0$ it equals $-K\Delta T-I^{2}R/2$, and at $x=L$ it equals $-K\Delta T+I^{2}R/2$, using $K=\kappa A/L$ and $R=\rho L/A$. Adding the local transported heat current $\alpha TI$ gives the two face equations. Summing equivalent legs preserves this accounting. Nonuniform material properties, side losses or asymmetric contact dissipation require a revised model.

For an original toy module, stipulate $\alpha =0.040V/K$, $R=2.0\Omega$, $K=0.40W/K$, $T_c=280\mathrm{K}$ and $T_h=300\mathrm{K}$. At $I=3.0\mathrm{A}$,The coefficient of performance is defined here only for refrigeration with $Q_c>0$ and $P_{\mathrm{in}}>0$. The hot-side assembly must remove $37.0\mathrm{W}$, not just the extracted $16.6\mathrm{W}$. These are stipulated calculations, not measurements or a commercial module specification.

At the same fixed face temperatures but $I=-3.0\mathrm{A}$, the same boundary definitions give $Q_c=-50.6\mathrm{W}$, $Q_h=-35.0\mathrm{W}$, $U=-5.2\mathrm{V}$ and $P_{\mathrm{in}}=15.6\mathrm{W}$. The formerly cold face is now heated; the formerly hot reservoir supplies $35.0\mathrm{W}$. Still $Q_h-Q_c=15.6\mathrm{W}$. Reversal changes the linear terms, while $I^{2}R$ and the leak at fixed temperatures remain unchanged. Holding the old labels fixed makes this check meaningful.

The corresponding steady entropy production of the module is the outgoing reservoir entropy minus the incoming reservoir entropy:The Peltier effect terms cancel because they carry the same entropy $\alpha I$ at each end. This cancellation explains the reversible coupling; it does not make finite-resistance operation reversible. In the toy example the two positive contributions are approximately $0.06214$ and $0.001905W/K$, giving ${\dot{S}}_{\mathrm{gen}}=0.06405W/K$ for either current direction. In cooling operation, combining this inequality with the energy balance gives the Carnot refrigerator limit $\mathrm{COP}\le T_c/(T_h-T_c)$, equal to $14$ for these reservoir temperatures. A coefficient of performance above one would describe transported heat per electrical work, not the creation of energy.

Thermoelectric cooling uses the Peltier effect to remove heat from a load using electrical work. A typical thermoelectric module connects many pairs of different semiconductors electrically in a series circuit and thermally in parallel between two faces. For an idealized pair with $S_p>S_n$, positive conventional current crosses n to p at the cold bridge and p to n at the hot return. With common bridge material and isothermal contacts, the intervening metal contributions telescope: the net pair coefficient is $S_p-S_n$. For $N$ identical pairs define the module Seebeck coefficient $\alpha =N(S_p-S_n)>0$.

Choose fixed face temperatures $T_h\ge T_c>0$, $\Delta T=T_h-T_c$, module electrical resistance $R>0$ and open-circuit thermal conductance $K>0$. All three module parameters $\alpha ,R,K$ are constants over the chosen operating range. Positive $I$ is the orientation absorbing Peltier effect heat at c. Define $Q_c$ as net heat extracted from the cold reservoir per unit time, $Q_h$ as net heat delivered to the hot reservoir per unit time, and $P_{\mathrm{in}}$ as electrical power entering the module. Despite the conventional letters $Q_c,Q_h$, both denote power in watts, not accumulated energy. Ferrotec gives the corresponding single-stage equations and distinguishes module performance from bypass leaks.^[ref]

A thermometer measures temperature through a physical response whose relation to temperature is known. Examples include the length change from thermal expansion, a change in electrical resistance, and the pressure of a gas thermometer. If the response function $X=f(T)$ is an injective function over the working range, its measured value determines $T=f^{-1}(X)$ through the inverse function. Thermometer calibration establishes that relation for the particular instrument and measurement conditions. Two matching readings are meaningful only after calibration to a common scale and with the probes sampling comparable equilibrium states. ^[ref]

For a contact thermometer, the sensing part must reach thermal equilibrium with the region being measured. That region may differ from the rest of the object: an immersed probe near a heater can read a local temperature while the surrounding water remains cooler. A stable reading can also be a steady state set by competing heat transfer paths to the sample and the room. Good contact, adequate immersion, mixing where appropriate, and checks for spatial differences help establish which temperature the reading represents. These are measurement controls inferred from the thermal equilibrium requirement, not a guarantee that every flat trace is equilibrium.

A thermometer also changes the sample it touches. Consider an original toy calculation with an initially uniform sample at $T_o=350\mathrm{K}$, a probe at $T_p=300\mathrm{K}$, and constant whole-body heat capacities $C_o=100\mathrm{J}{\mathrm{K}}^{-1}$ and $C_p=1\mathrm{J}{\mathrm{K}}^{-1}$. Suppose together they form an isolated system, with no work or phase transition and negligible contact energy. The first law of thermodynamics and thermal equilibrium giveThe final thermometer reading underestimates the sample's original temperature by about $0.495\mathrm{K}$, although it correctly measures their new common temperature. The disturbance becomes small when the participating probe heat capacity is small compared with the sample's. A large controlled heat bath is a different limit: it supplies or removes heat while approximately maintaining its own temperature.

Waiting time is a separate issue from disturbance. Under a toy Newton's law of cooling model for a uniform probe in a maintained heat bath, a constant contact conductance $G$ givesThe time constant $\tau$ controls this exponential decay. For stipulated values $T_b=350\mathrm{K}$, $T_p(0)=300\mathrm{K}$ and $\tau =5\mathrm{s}$, the probe reads about $331.61\mathrm{K}$ after one time constant and $347.51\mathrm{K}$ after three. These are calculated values, not an instrument specification or measured data. Real probes may have multiple relaxation times and additional heat transfer paths; choose an equilibration criterion from the required accuracy, rather than assuming that a fixed waiting time works universally.

A useful original model treats the thermopile absorber as one approximately uniform temperature $T_h(t)$ with heat capacity $C_{\mathrm{th}}$, connected to a fixed reference temperature $T_c$ by thermal conductance $G_{\mathrm{th}}$. Both parameters are positive constants here. Let $P_{\mathrm{abs}}(t)$ be an added absorbed power above the initial background. Linearize the outgoing heat transfer about that background. With $\Delta T=T_h-T_c$ measured from an initial state having $\Delta T=0$, conservation of energy gives the first-order linear differential equationThe left side is the rate of stored energy; the two terms on the right are added power and outgoing heat transfer. The effective thermal conductance can include several paths, rather than just heat conduction along the wires. The model assumes a stable reference, negligible electrical loading, a common absorber temperature, and changes small enough for constant parameters.

For a step from zero to constant $P_0$ at $t=0$, subtract the steady solution $\Delta T_{\infty }=P_0/G_{\mathrm{th}}$. The difference obeys exponential decay, so the initial condition fixesThe time constant has units $(\mathrm{J}{\mathrm{K}}^{-1})/(\mathrm{W}{\mathrm{K}}^{-1})=\mathrm{s}$. With the same constructed $N=20$ and $\alpha =40\mu \mathrm{V}{\mathrm{K}}^{-1}$, choose $C_{\mathrm{th}}=0.02\mathrm{J}{\mathrm{K}}^{-1}$, $G_{\mathrm{th}}=0.01\mathrm{W}{\mathrm{K}}^{-1}$ and $P_0=0.03\mathrm{W}$. ThenAt one time constant, the response is $1-e^{-1}\approx 0.632$ of its final value: $V_{\mathrm{oc}}(2\mathrm{s})\approx 1.52\mathrm{mV}$. Reaching $95\%$ requires $t=-\tau \ln (0.05)\approx 5.99\mathrm{s}$. A voltmeter read too soon therefore underestimates the steady signal even when its electrical calibration is perfect.

The steady ratio $V_{\infty }/P_0=N\alpha /G_{\mathrm{th}}$ is $0.080\mathrm{V}{\mathrm{W}}^{-1}$ in this constructed model. Halving thermal conductance doubles this ratio but also doubles the time constant if heat capacity stays fixed. Reducing heat capacity alone speeds the response without changing its steady value. Increasing $N$ gives a larger signal only at fixed individual temperature differences: adding legs can also change thermal conductance, heat capacity and electrical resistance. The algebra identifies coupled design choices, rather than predicting a particular manufactured detector.

A finite electrical resistance produces Thermal electrical noise. For nearly uniform absolute temperature $T$ and effective measurement signal bandwidth $B$, its root mean square open-circuit voltage isHere $k_{\mathrm{B}}$ is the Boltzmann constant. Thermal electrical noise in the sensing element is an important contribution, and the signal bandwidth enters its voltage variance.^[ref] If identical pairs have fixed electrical resistance $r$ and fixed $\Delta T$, then $R_{\mathrm{pile}}=Nr$: the signal grows as $N$ while this noise grows as $\sqrt{N}$. The resulting signal-to-noise ratio grows only as $\sqrt{N}$ under those assumptions. Reference temperature drift, environmental electromagnetic radiation, and meter noise remain separate limits; reducing signal bandwidth trades fast information for less integrated electrical noise.

With ${ϵ}^{01}=+1$, the Noether density for the angular shift gains $\theta {\partial }_x\cos \varphi /(4\pi )$. Its integral gives the displayed topological shift. Mechanical charge $Q_0$ determines the classical rotating-kink energy, while canonical symmetry charge $Q_{\theta }$ is conjugate to the periodic angle and is integral after quantization. Reversing the epsilon convention reverses the theta sign.

Locally this density is a total derivative, so it changes neither the bulk field equations nor the energy. Its contribution to the angular canonical momentum is a spatial boundary derivative. With ${ϵ}^{01}=+1$, it produces the theta-angle shift of a sigma-model kink charge.

At fixed gradient and magnet length, the signed thin-lens focal length is proportional to particle momentum. For total energy error $\delta =(E-E_0)/E_0$, differentiating $p^2{c}^2=E^2-m^2{c}^4$ gives $d\ln p/d\ln E=1/{\beta }^2$. The ultrarelativistic result is $f=f_0(1+\delta )$ to first order. If energy means kinetic energy instead, the coefficient is $(K+m{c}^2)/(K+2m{c}^2)$.

Let a strong shock wave of radius $R$ and speed $V$ sweep a uniform mass density ${\rho }_0$ into a shell of mass $4\pi {\rho }_0{R}^3/3$ and speed $2V/(\gamma +1)$. If the cavity pressure is $\alpha$ times the immediate post-shock pressure, shell momentum balance gives $R\dot{V}=3(\alpha -1)V^2$. Constant total energy gives $R^3{V}^2=\mathrm{constant}$ and hence $\alpha =1/2$. Including shell internal and kinetic energy, and treating the cavity volume as $4\pi R^3/3$ to thin-shell accuracy, yields $R=\xi (E/{\rho }_0{)}^{1/5}{t}^{2/5}$ with ${\xi }^5=75(\gamma -1)(\gamma +1{)}^2/[16\pi (5\gamma -3)]$. This coefficient is approximate; resolving the shell's finite volume changes it.

Combine the two massless neutrinos in ${\tau }^{-}\to {\ell }^{-}{\bar{\nu }}_{\ell }{\nu }_{\tau }$ into $q$. In the parent rest frame, four-momentum conservation givesThe lower bound follows from the nonnegative Minkowski norm of the sum of two future-directed null four-vectors; the upper bound follows from $E_{\ell }^{\ast }\ge m_{\ell }$. Substituting gives the displayed energy bounds. They are kinematic: they do not specify the weak interaction decay amplitude or the probability density function inside the interval.

If the charged daughter is also massless, put $x=2E_{\ell }^{\ast }/m_{\tau }\in [0,1]$. A parent with Lorentz factor $\gamma$ and speed $\beta$ in natural units producesHere ${\theta }^{\ast }$ is the daughter angle relative to the boost direction in the parent rest frame. Two opposite parent momenta therefore need not produce two opposite visible daughter momenta: the invisible system can recoil differently in each particle decay.

For the uniform noninteracting electron model with two spin states and kinetic energy of nonrelativistic particles $E=p^2/(2m_e)$, count all available one-particle states up to an energy $E\ge 0$:This extensive density of states has units of inverse energy; $g(E)/V$ is the density of states per unit volume. Availability and occupation are different: $g(E)$ is positive above $E_F$, but at zero temperature those states are empty. The occupied energy distribution is $g(E)f(E)$, with the Fermi-Dirac distribution reduced to $f(E)=1$ below $E_F$ and $f(E)=0$ above it. The convention at the exact boundary does not affect a continuum integral.

With the dimensionless quantity $x=E/E_F$, the occupied count per $dx$, divided by the total particle number, is $3\sqrt{x}/2$ for $0<x<1$. Its area is one. Weighting this by $E$ gives the internal energy and its mean per particle:Thus the highest occupied energy and the mean energy differ. For the Fermi energy of a model electron gas, $U/N\simeq 1.0155\mathrm{eV}$. At fixed $N$, $E_F\propto V^{-2/3}$, so the derivative $P=-(\partial U/\partial V{)}_N$ gives the electron degeneracy pressure $P=2n{E}_F/5$. The same state-counting geometry therefore predicts a nonzero pressure at zero temperature.

For isotropic direct-gap parabolic bands, $m_r^{-1}=m_e^{\ast -1}+m_h^{\ast -1}$ and transition energy is $E_g+{\hslash }^2{k}^2/(2m_r)$. Differentiating the two-spin state count $k^3/(3{\pi }^2)$ per volume gives the displayed density for $E>E_g$, and zero below. Density per angular frequency is $\hslash g_j(\hslash \omega )$, not the same dimensioned quantity.

In a minimal hole description of a metal–ligand–metal path, two holes initially occupy separate metal orbitals and the ligand has no hole. Creating a virtual ligand hole costs a charge-transfer energy $\Delta$. Two hops generate an effective metal–metal hopping of order $t_{pd}^2/\Delta$; two more hops through metal double occupancy generate the antiferromagnetic scale in the title. Ligand double occupancy adds a channel with denominator $2\Delta +U_p$. Orbital geometry and intra-atomic exchange determine when the antiferromagnetic channel dominates.

In an orthonormal basis of localized atomic orbitals, a ring of three equivalent sites with real hopping $t$ has Hamiltonian $H=(E_0-t)I+tJ$, where $J$ is the three-by-three all-ones matrix. The normalized symmetric state $(|1⟩+|2⟩+|3⟩)/\sqrt{3}$ has energy $E_0+2t$. Its two-dimensional orthogonal complement has energy $E_0-t$. Thus the symmetric state is the unique spatial ground state for $t<0$, with an energy difference $3|t|$ to the excited eigenstates. Equivalently, the three discrete Bloch states have energies $E_0+2t\cos (2\pi l/3)$, $l=0,\pm 1$. Nonorthogonal atomic orbitals instead require a generalized eigenvalue problem.