In a classically forbidden region, the Schrödinger equation has evanescent solutions rather than forcing the wavefunction to vanish. Matching at both sides of a finite barrier permits nonzero transmission. For a broad barrier the WKB approximation gives
where is a matching prefactor. Transmission is exponentially sensitive to barrier width and height. A single decaying exponential function carries no probability current; the matched scattering solution includes the combination needed for transmitted current. energy is conserved throughout.
In alpha decay, a quasibound alpha particle penetrates the nuclear Coulomb barrier. Multiplying the penetration probability by an assault frequency estimates the decay rate; the strong dependence on alpha energy explains the wide range of lifetimes. In a scanning tunnelling microscope, a voltage drives electron quantum tunnelling between a conducting tip and sample. Approximately , so constant-current feedback resolves changes in gap width, with electronic density of states also affecting the image. Piezoelectric motion, vibration isolation and stable voltage are necessary; a bright feature is not automatically a taller atom. Atomic-scale imaging was demonstrated with a vacuum-tunnelling microscope in the original surface study.[ref] In a Josephson junction, Cooper pair quantum tunnelling through a weak link gives , allowing supercurrent without an applied voltage and phase-sensitive interference. These are distinct applications of barrier penetration and coupling with quantum coherence, not particles borrowing energy to climb over a barrier.
With periodic boundary conditions, each state occupies volume and has two spin states. Filling a sphere gives and
Here is density of states per volume and per energy; the extensive is . Both spin states are already included.
For divalent magnesium, , giving
At , only electrons within about of the Fermi surface change occupancy. The Sommerfeld heat capacity is
Equivalently , with in kelvin, so at room temperature it is about . A temperature was not specified for the estimate; the linear coefficient is the general result.
At sufficiently low temperature, an ordinary nonsuperconducting metal has : electrons dominate at the lowest temperatures, acoustic phonons produce the cubic contribution, and the lattice approaches per mole as temperature exceeds its characteristic Debye scale. Anharmonic expansion can distinguish measured from . In the room-temperature regime, since , so electron excitation is strongly Pauli-limited. The free-electron estimate is only about of the classical lattice scale. Calling it negligible means small relative to the lattice contribution, not identically zero or negligible as . Real band structure and interactions can alter the coefficient.
Figure 1.
Original illustrative metal heat-capacity regimes: Sommerfeld linear electrons and Debye phonons, with explicit dimensionless model parameters
. Details.
spin normalization in two-dimensional free-electron state counting. Treat the mobile electrons as independent particles in a constant interior potential, with parabolic dispersion , and impose confinement or periodic boundary conditions. electron–electron interactions and the detailed periodic ionic potential are neglected, while Fermi statistics are retained. Each spatial state occupies area in two-dimensional wavevector space. For spin degeneracy ,
The printed coefficient is the per-spin density of states. Unpolarized spin-one-half electrons have , doubling it. Actual graphene near its Dirac points has approximately linear dispersion, so its energy-dependent density of states is not this parabolic-model result; the plane geometry alone does not establish the free-electron dispersion.[ref]
Occupied disk and Fermi energy. At zero temperature fill the lowest states up to a disk of radius . State counting gives
Thus the physical spin-degenerate result is . If instead counts one spin species, the per-spin convention gives . Each occupied wavevector can contain one electron of each allowed spin, never two in the same complete one-particle state.
Figure 1.
Original occupied wavevector disk and Fermi-Dirac occupations for a parabolic two-dimensional electron gas
. Details.
Occupation probability and chemical potential of a two-dimensional ideal Fermi gas. A single fermion state permits occupation zero or one. In a grand canonical ensemble their relative weights are and . Normalizing gives
The chemical potential is fixed by the total particle number. Here the total density of states is constant above the band bottom. Integrating the occupation gives , and therefore
The approach is exponentially close in this ideal two-dimensional constant-density-of-states model; a three-dimensional correction should not be inserted here. A narrow interval of width of order around is thermally smeared.
The Debye model replaces the crystal by a harmonic elastic continuum with acoustic dispersion . It counts three polarizations and introduces a cutoff so that the total number of vibrational modes is , where is the atom count. Periodic-box counting gives
For an isotropic average speed, . With cutoff frequency fixed by the mode count,
This density of states is quadratic because a three-dimensional shell has volume proportional to and the acoustic dispersion is linear. The cutoff is a mode-counting device; it is not a claim that every actual branch stays linear to the zone boundary.
Each phonon mode has mean thermal energy , using Bose-Einstein statistics with zero phonon chemical potential. The fixed harmonic zero-point contribution has zero temperature derivative. With ,
and differentiating at fixed volume gives
For , extend the upper limit to infinity. Expanding gives . integration by parts makes the heat-capacity integral , so
Only modes with are appreciably excited; their number scales as , explaining the power law physically. At high temperature every mode contributes , giving the Dulong-Petit limit .
The model assumes the harmonic approximation, a macroscopic three-dimensional solid and acoustic continuum behaviour for the thermally populated modes. Anisotropic sound speeds change the low-temperature coefficient rather than its cubic power. Real optical branches and nonlinear acoustic dispersion limit the full-temperature approximation; electronic excitations can add a linear term in a metal, and anharmonicity produces thermal expansion and distinctions between and . At temperatures below the lowest finite-sample mode, the bulk continuum law also fails. Thus the result is the low-temperature lattice contribution, not a universal total heat capacity for every solid.
The mean energy of a two-dimensional Fermi gas follows from its constant density of states for nonrelativistic quadratic dispersion. At zero temperature, states below are filled, so
The Pauli exclusion principle confines thermally excited conduction electrons to an energy interval of order around the Fermi surface. Their excess energy is therefore proportional to , giving an electronic heat capacity . More precisely, . In a three-dimensional Debye model, acoustic phonons have density of states proportional to ; their thermal energy scales as , giving
per mole of atoms. This assumes a normal metal without a lower-temperature superconducting or magnetic anomaly.
For , the lattice approaches the Dulong-Petit value, so , usually dominated by . Each classical vibrational mode contributes through kinetic and potential equipartition. This is a high-temperature solid-state regime, not a claim that the solid persists to arbitrarily high temperature; anharmonicity and can matter.
The body-centred cubic cell has two atoms, so . Counting three acoustic branches gives . By the Debye-temperature definition,
This is an effective Debye sound speed; separate longitudinal and transverse speeds are not determined. For isotropic branches, .
Quantum tunnelling is supported by transport and decay through barriers that classical particles of the same energy cannot traverse. Three complementary examples are:
Together these test barrier penetration in nuclear decay, vacuum-gap transport and semiconductor transport. Their detailed currents depend on state supply and matching as well as the barrier transmission probability.
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.
Only a shell of energy width of order near the Fermi energy can change occupation: much lower states are blocked by the Pauli exclusion principle. The thermal-shell estimate of electronic heat capacity counts
To recover the rough coefficient requested in the paper, assign each of these active particles an excitation energy of order . Then
The differentiation matters: the active shell itself widens as temperature rises. This argument explains the small linear-in- electronic heat capacity; its shell width and average excitation energy are heuristic, so it does not establish a precise numerical prefactor.
A controlled calculation from the Fermi-Dirac distribution gives a nearby but different result. At fixed particle number, the Sommerfeld expansion yields
Thus is a rough estimate of the exact free-electron coefficient , not an exact consequence of the stated density of states. Both require .
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.
For a plane wave wavefunction , impose the cyclic or periodic boundary condition . It requires
Adjacent allowed wavenumbers on the full signed axis are spaced by . Ignoring spin, the density of states per unit is consequently
Both positive and negative are included in this density. It is not yet the density per unit magnitude , which has an extra factor of two away from zero. In independent dimensions the same periodic boundary conditions give one spatial state per -space cell of measure .
In three dimensions use the -space density of states per spin species and the spherical shell volume :
Thus the three-dimensional free-electron density of states grows as . For physical electrons, including both spin states gives
All three total density of states functions have units when energy is in joules; they count states per energy interval. The paper explicitly suppresses spin in (a) but does not repeat that convention in (b), so giving both conventions avoids a hidden factor-of-two ambiguity. Parts (c)--(f) below use the physical two-spin-state electron gas.
In two dimensions the density of states in space per spin species is . A annulus of radius and thickness has area . Therefore
The two-dimensional free-electron density of states is constant in energy, , above the band bottom. Including both spin states gives . Dividing by gives the density per unit physical area, rather than the total specimen's density.
Let and take a specimen of length, area or volume . One monovalent atom per unit cell supplies
electrons. At zero temperature, the Pauli exclusion principle fills the lowest energy states, with two spin states per spatial wavevector. The occupied region is an interval, disk or ball of radius . Using the -space density of states gives, in one dimension,
In two dimensions,
In three dimensions,
Each Fermi energy follows from the free electron model dispersion relation . The Fermi wavevectors have units and the Fermi energies have units joules for in metres and in kilograms. No numerical lattice spacing is supplied, so numerical energies in electronvolts cannot be uniquely calculated. The spin factor of two is necessary here for actual monovalent crystals; the spinless auxiliary count of part (a) was not an instruction to remove electron spin from these crystals.
Keep the electron number fixed, so
and . Heating smooths the Fermi-Dirac distribution across the Fermi energy, creating holes below and particles above it. The sign of the low-temperature adjustment of chemical potential follows from the local slope of the density of states.
In one dimension, decreases with energy. At fixed , smoothing removes more electrons below it than it adds above it, so initially rises. In three dimensions, increases, so falls. In two dimensions the constant density of states makes the leading changes cancel, so stays extremely close to in the degenerate regime.
For quantitative checks, a Sommerfeld expansion gives, for ,
For a constant two-dimensional density of states above an unbounded parabolic band bottom, the number integral can be done exactly:
so
It actually decreases, but its low-temperature correction is exponentially small rather than quadratic. “Constant in two dimensions” is therefore a low-temperature approximation, not an exact statement for every .
The one-dimensional rise is also only an initial trend. In the high-temperature Maxwell-Boltzmann distribution limit, the ideal -dimensional electron gas has , where and is the thermal de Broglie wavelength. It eventually becomes negative and decreases in every dimension. The one-dimensional chemical potential thus passes through a maximum. This high-temperature statement refers to the stipulated unbounded free-electron dispersion relation, not a claim that a real finite-width crystal band remains parabolic indefinitely.
Let two weakly coupled bodies exchange energy while their total energy is fixed. If body1 has , the number of compatible states is . Its most probable equilibrium division maximizes the logarithm, giving
This equal intensive quantity labels thermal equilibrium. With and thermodynamic ,
Ordinary positive heat capacities make the entropy maximum locally stable. Particle numbers and volumes are held fixed during the exchange.
For a subsystem coupled to a large heat bath, the exact level weight is proportional to . Expanding the bath entropy gives . Normalization therefore gives
The Boltzmann form uses the reservoir limit; an arbitrary small isolated pair instead retains its exact bath state count. The degeneracy counts distinct subsystem microstates at the same energy, rather than adding another Boltzmann factor for the whole level.
In the two-level donor occupancy model, set the single bound-state energy to zero and the conduction representative to with degeneracy . Ignoring spin, its bound probability is
The measured model occupancy gives , so
using . The supplied occupancy and energy are rounded, so there is no reason to demand an exact nonrounded integer from that inference.
For , the excited-to-bound weight must be . Eliminate using the first point:
The probability decreases monotonically from1 as toward as . The nonzero high-temperature limit follows from the stipulated finite effective degeneracy, not from a full continuum conduction-band calculation. A realistic band with energy-dependent density of states need not retain this two-level limit.
Figure 1.
Donor occupancy
. Two-level model with both inferred temperature points. Details.
Equilibrium radiation and cavity frequencies. A blackbody absorbs all incident radiation at every frequency and direction. In thermal equilibrium its emission spectrum depends only on its temperature. Radiation inside an isothermal absorbing cavity, sampled through a small aperture that hardly disturbs equilibrium, realizes black-body radiation to a good approximation. Microscopic absorption and emission establish the equilibrium distribution; a perfectly reflecting wall is the convenient idealization used to count the modes once that distribution is specified.
In a rectangular electromagnetic cavity, the wave equation and perfect conductor wall boundary conditions select component wavenumbers , , . Combining the vacuum dispersion relation and gives
For example, electric-field components can have the spatial dependence
For three positive indices, Gauss's law requires , leaving two independent polarizations of an electromagnetic wave.
Index qualification. The original paper describes the indices as positive integers. That describes the three-nonzero-index family but omits valid electromagnetic modes with exactly one zero index, which have one polarization of an electromagnetic wave. For instance, with , , only above remains; it is normal to the top and bottom faces and vanishes at the side walls. Two zero indices give no nontrivial cavity field. The omitted one-zero-index family does not affect the leading three-dimensional mode count, but is essential to the thin-cavity limit below. Retaining the paper's strict positivity restriction for every mode would instead give a thickness gap and would not yield its requested two-dimensional power law.
Three-dimensional mode count. A lattice cell in positive space has volume , where . In a continuum approximation, a shell of radius and thickness contains its positive octant, multiplied by two polarizations:
Using gives
For a finite cavity the exact density of states is discrete; this formula is its bulk continuum limit, appropriate when many modes contribute and wall corrections are small.
Mean photon number. A mode is a quantum harmonic oscillator with thermal excitation energies , . The zero-point energy does not enter its thermal occupation. Put . Its partition function and mean occupation are
This is the Bose-Einstein distribution with zero photon chemical potential: equilibrium absorption and emission do not conserve photon number.
Thermal energy. Multiply the density of states by the mean excitation energy and integrate:
The substitution isolates all the dependence on cavity dimensions and temperature:
Expanding gives an integral . Hence
This is the thermal energy only, excluding the zero-point contribution. The three-dimensional continuum regime requires large compared with the geometric level spacings in all three directions.
Spectral sketch. The spectral energy density per unit ordinary frequency is Planck's law,
At small frequency it rises as , while at large frequency it decays exponentially. Raising temperature increases the spectrum at every fixed positive frequency, moves the peak to larger frequency in proportion to , and increases the integrated area in proportion to . A plot per unit wavelength has a different peak position because the integration variable changes.
Figure 1.
Planck spectral energy density at three temperatures on common frequency and energy-density scales
. Original plots of the frequency spectrum, with temperatures in the ratios 1:1.5:2. The dimensionless horizontal axis is hν/(kBTref), and the vertical scale is common to all curves. The higher-temperature peak moves right and the area grows as T to the fourth power. Details.
Thin-cavity radiation. Let . The relevant low-temperature window is
Nonzero thickness indices are then thermally suppressed, while many in-plane modes are populated. The family has one polarization of an electromagnetic wave. Its allowed in-plane wavenumbers form a lattice of cell area ; a quarter of a circular shell therefore contains
Thus the dimensional crossover of thermal cavity radiation gives
The integral is by the same geometric-series argument. A model with a different number of independent polarizations of an electromagnetic wave changes the prefactor but not the scaling. For a cavity with fixed finite , cooling still further eventually freezes its lowest in-plane mode as well: the strict thermal energy is exponentially suppressed. The requested area law is the intermediate quasi-two-dimensional regime, not an arbitrarily low-temperature continuum limit.
A cubic reflecting cavity supports standing waves with positive integer mode indices and wavevector components . A cell in mode space has volume . In the continuum approximation, a spherical shell of radius and thickness has one-eighth of its volume in the positive octant. There are two independent transverse photon polarizations for a generic wavevector. Hence
The photon energy is , so . Therefore
This is the leading bulk density of states, valid when the cavity is large compared with the relevant wavelengths and many modes lie in the counting interval. A finite cavity has a discrete mode spectrum, with boundary corrections beyond this approximation. Modes with vanishing indices require separate boundary counting but do not change the leading term. Here is the reduced Planck constant, as printed in the original PDF; replacing it by would introduce an erroneous factor of .
Each independent cavity mode is a quantum harmonic oscillator of angular frequency . Its occupation numbers represent the numbers of photons in that mode. At thermal equilibrium, photons can be absorbed and emitted by the walls, so their number is not conserved and the photon chemical potential is zero. The Boltzmann distribution of the oscillator excitations then gives
The expression supplied in the paper is the thermal excitation energy. The oscillator's temperature-independent zero-point energy is excluded from the emitted thermal radiation.
Putting and into the mode count from (a) gives the number of modes per unit cavity volume:
Multiplying by the mean thermal energy in each mode yields Planck's law in the angular-frequency convention:
The two photon polarizations are already included in the density of states; no further factor of two is needed. has units , whereas has units .
For the usual nonrelativistic dispersion, the three-dimensional density of states is . Filling all states through the Fermi energy gives
Degeneracy factors cancel. More generally gives ; an ultrarelativistic gas would give . The nonrelativistic result is the standard massive ideal-gas interpretation.