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A band effective mass describes the acceleration of an electronic wavepacket in a periodic lattice through the local band curvature. It incorporates the periodic lattice potential into a useful transport parameter without changing the bare electron mass. For a Bloch state in an isolated band,Differentiation givesIn one dimension this becomes $\boxed{m^{\ast }={\hslash }^2/(d^2ϵ/d{k}^2)}$. A locally parabolic isotropic band minimum has $ϵ\simeq {ϵ}_c+{\hslash }^2|\mathbf{k}-{\mathbf{k}}_c{|}^2/(2m^{\ast })$ with positive $m^{\ast }$. A flatter band has a larger effective mass. At a band maximum the electron curvature is negative, so the electron accelerates oppositely to the applied force. Describing the missing electron as a positive-charge electron hole with positive mass is often simpler.

In the scalar relaxation-time approximation, a conduction electron in an electric field reaches ${\mathbf{v}}_d=-e\tau \mathbf{E}/m^{\ast }$. ThusFor a crystal with different directional curvatures, conductivity is a tensor and involves the occupied states and their scattering. Contributions from electrons and holes add: $\sigma =e(n{\mu }_e+p{\mu }_h)$ in an isotropic two-carrier description. A filled band contributes no ordinary longitudinal current because opposite group velocities cancel; a partially filled band or holes permit a current response.

Effective mass therefore connects measured electrical transport to electronic band structure, but carrier density and momentum relaxation time matter as much as curvature. Ionised impurities and phonons alter $\tau$. A smaller mass does not guarantee a higher conductivity if carrier population or scattering changes. Nor are all reported masses identical: density-of-states, cyclotron and conductivity masses weight anisotropic bands differently. The simple semiclassical formula assumes an isolated band, slowly varying weak fields and negligible interband transitions; near degeneracies or strong fields a single constant scalar mass is inadequate.

For a Bravais lattice with primitive translation vectors ${\mathbf{a}}_1,{\mathbf{a}}_2,{\mathbf{a}}_3$, define the reciprocal lattice by vectors $\mathbf{G}$ satisfying $e^{i\mathbf{G}\cdot \mathbf{R}}=1$ for every direct-lattice translation $\mathbf{R}$. A convenient basis iswith cyclic formulas for ${\mathbf{b}}_2,{\mathbf{b}}_3$. Then ${\mathbf{a}}_i\cdot {\mathbf{b}}_j=2\pi {\delta }_{ij}$ and $\mathbf{G}=h{\mathbf{b}}_1+k{\mathbf{b}}_2+l{\mathbf{b}}_3$ for integers $h,k,l$. The reciprocal primitive volume is $(2\pi {)}^3/V_{\mathrm{cell}}$.

These vectors are the spatial Fourier series frequencies of a periodic lattice potential or density. Elastic coherent crystal diffraction occurs when the scattering wavevector transfer equals a reciprocal lattice vector, with intensities additionally controlled by the basis crystal lattice structure factor. This is the reciprocal-space version of Bragg's law. A lattice of points and its basis should not be confused: a basis can make allowed reciprocal-lattice diffraction intensities vanish.

The first Brillouin zone is the Wigner-Seitz cell around the reciprocal origin: it consists of points closer to $\mathbf{G}=0$ than to any other reciprocal point. Its faces lie on the perpendicular bisectorsTo see the condition, equate $|\mathbf{k}{|}^2$ and $|\mathbf{k}-\mathbf{G}{|}^2$. These are also free-electron Bragg-degeneracy planes, where a periodic potential can open a band gap. Higher zones classify regions beyond successive Bragg planes; the reduced-zone description folds them into the first zone while retaining a band label.

In one dimension with spacing $a$, reciprocal points occur at $2\pi j/a$, and the first zone is $[-\pi /a,\pi /a]$. A square lattice of spacing $a$ has reciprocal basis $2\pi \hat{\mathbf{x}}/a,2\pi \hat{\mathbf{y}}/a$, and a square first zone with edges at $k_x,k_y=\pm \pi /a$.

The reciprocal of a face-centered cubic lattice is a body-centered cubic lattice and vice versa, with the scale fixed by the primitive-vector definition. In a Bloch state, wavevectors differing by $\mathbf{G}$ describe equivalent crystal momenta modulo the lattice periodicity. A crystal with $N$ primitive cells has $N$ allowed wavevectors in one Brillouin zone, hence $N$ states in each band per spin. This state count links reciprocal geometry to band filling, metallic conduction and band insulating behaviour. Reciprocal space also labels phonons and makes conservation of crystal momentum modulo $\hslash \mathbf{G}$ transparent.

A Bloch state in a crystal experiences a periodic lattice potential. Its band dispersion relation $ϵ(k)$ encodes the lattice response, so an effective mass allows a wavepacket's acceleration under a weak applied force to be described without explicitly following the microscopic periodic forces.

In one dimension the wavepacket group velocity and semiclassical equation for crystal momentum areDifferentiating the first equation with respect to time givesDefining $F=m^{\ast }a$ yieldsThis band effective mass is controlled by band curvature, not the slope. A band minimum has positive $m^{\ast }$; a band maximum has negative electron $m^{\ast }$ and is often more conveniently described with positive-mass electron holes. In three dimensions the inverse effective mass is generally a tensor, $(m^{\ast -1}{)}_{ij}={\hslash }^{-2}{\partial }_{k_i}{\partial }_{k_j}ϵ$. The scalar formula assumes motion along a specified direction in an isolated band, weak fields and negligible interband transitions; the bare electron mass has not physically changed.

The quantum free electron model treats conduction electrons as independent particles moving in an approximately constant potential, with parabolic dispersion relation $E={\hslash }^2{k}^2/(2m)$. Fermi-Dirac statistics successfully explains important features such as a Fermi energy and a small electronic heat capacity, but a constant potential gives no band gaps and cannot by itself explain why different band fillings produce metals, semiconductors and band insulators. It also misses lattice-dependent effective masses, detailed directional responses and the topology of real Fermi surfaces. Scattering and finite electrical resistivity require additional physics.

The nearly-free electron model introduces a weak periodic lattice potential. Bloch's theorem replaces individual free plane waves by Bloch states, and Fourier components of the potential mix plane waves whose wavevectors differ by a reciprocal lattice vector. Near degeneracy at a Brillouin zone boundary, this coupling opens a band gap; for a two-wave crossing its size is $2|V_G|$. Away from the crossing, energies remain close to free-particle values. Band curvature produces band effective masses, and band filling determines whether the Fermi energy lies inside an allowed band or a gap.

The improvement is the inclusion of lattice periodicity, rather than a switch from classical to quantum statistics: the quantum free electron model already uses Fermi-Dirac statistics. The strong delta barriers in the later numerical example are treated exactly by the Kronig-Penney model, rather than by assuming that their strength is perturbatively small.

A Bloch state on the loop has $\psi (x)=u(x)e^{i\varphi x}$, with $u(x+a)=u(x)$. Its circumference is $L=Na$, so $u(x+Na)=u(x)$. Single-valuedness after one complete circuit requires the periodic boundary conditionThereforeThe allowed Bloch wavevectors are spaced by $2\pi /(Na)$. Values of $\varphi$ differing by $2\pi /a$ label the same crystal momentum modulo a reciprocal lattice vector, so there are $N$ inequivalent choices in one Brillouin zone. In this notation $\varphi$ is the Bloch wavenumber, not a dimensionless phase; $\varphi a$ is dimensionless. Spin gives additional states but does not alter this condition.

Let $N=L/a$ be the integer number of primitive unit cells. A Bloch state can be written as ${\psi }_k(x)=e^{ikx}{u}_k(x)$, with $u_k(x+a)=u_k(x)$. The periodic boundary condition ${\psi }_k(x+L)={\psi }_k(x)$ therefore requiresThe spacing of allowed wavevectors is $\Delta k=2\pi /L$. The first Brillouin zone has width $2\pi /a$, soFor an exact endpoint convention take a half-open Brillouin zone, such as $[-\pi /a,\pi /a)$. Its two endpoints differ by a reciprocal lattice vector and must not both be counted as distinct values of crystal momentum. There are exactly $N$ inequivalent integers $j$ modulo $N$, irrespective of whether $N$ is even or odd. This is state counting in a Bloch band: one allowed wavevector per primitive unit cell per energy band. A separate twofold spin multiplicity gives $2N$ electronic states per energy band, without doubling the number of wavevectors.

The crystal has periodic potential $V(x+a)=V(x)$. By Bloch's theorem, an energy eigenstate may be chosen asExpand the periodic factor in a Fourier series:Multiplication by $e^{ikx}$ gives the stated plane-wave expansion. Here $x$ is position, $a$ is the primitive unit cell length, $G_1$ is the primitive reciprocal lattice wavenumber, $n$ runs over every integer, and $C_{k,n}$ are complex numbers specifying the component wave amplitudes. The wavevector $k$ labels the Bloch state modulo $G_1$; $\hslash k$ is its crystal momentum, rather than generally its measured free-space momentum.

The component $e^{i(k+n{G}_1)x}$ is a plane wave of wavevector $k+n{G}_1$. All these components acquire the same phase factor $e^{ika}$ under $x\mapsto x+a$, since $e^{in{G}_{1}a}=1$. Their mixing therefore respects the crystal's translation symmetry. The coefficients and energy eigenvalue follow from the Schrödinger equation; the expression is not a claim that the coefficients are equal or that only finitely many are nonzero. The energy band index is suppressed in the notation, so different energy bands at a common $k$ generally have different coefficient sets.

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.

In the Bloch wave sum, $N$ is the number of sites, $R_j=ja$ the equilibrium position of site $j$, $\varphi (r-R_j)$ a localized atomic orbital there, and $k$ the crystal wavevector. The phase factor gives the translation character of the Bloch state. The factor $1/\sqrt{N}$ normalizes it when the site orbitals are treated as orthonormal; appreciable intersite overlap requires an overlap-dependent normalization.

For a tight-binding model, choose localized orbitals and calculate the on-site and intersite Hamiltonian matrix elements. Form Bloch sums for each orbital type and solve $H(k)c=E(k)S(k)c$ at each $k$, where $S(k)$ is the orbital-overlap matrix. In the orthogonal tight-binding approximation, $S=I$. The eigenvalues give the energy bands and the eigenvectors their orbital composition; the nonorthogonal nearest-neighbour tight-binding band illustrates how retained overlap modifies this procedure.

For one orthonormal s orbital per site, keep on-site energy ${ϵ}_s$ and real nearest-neighbor hopping integral $t=⟨{\varphi }_j|H|{\varphi }_{j+1}⟩$. The two neighbors contribute phases $e^{\pm ika}$, giving $E_s(k)={ϵ}_s+2t\cos ka$. The band-curvature definition $1/m^{\ast }=E^{\prime \prime }(k)/{\hslash }^2$ givesWith the usual bonding convention $t<0$ for these s orbitals, the center is a minimum with positive electron effective mass and the edge a maximum with negative electron effective mass. Hole masses near a filled-band maximum have the opposite sign.

For p orbitals aligned along the chain, the orbital phase and the sign of one-dimensional hopping reverse the usual center-versus-edge ordering. Choose every $p_x$ orbital with its positive lobe on the right. Equal neighboring Bloch coefficients then bring opposite-sign lobes together between sites, giving an antibonding state at $k=0$. Alternating coefficients at $k=\pi /a$ make those facing lobes have the same sign, producing the lower bonding state. Thus a nearest-neighbor model has $E_p(k)={ϵ}_p+2t_{\sigma }\cos ka$ with the usual $t_{\sigma }>0$, maximum at zero and minima at the zone edges. This uses a fixed common orbital-phase convention at all sites.

Let the missing electron occupy the Bloch state of crystal momentum $\hslash {\mathbf{k}}_e$ and energy $E_e({\mathbf{k}}_e)$. Relative to the filled band, define ${\mathbf{k}}_h=-{\mathbf{k}}_e$ modulo a reciprocal-lattice vector and $E_h({\mathbf{k}}_h)=C-E_e(-{\mathbf{k}}_h)$, with a fixed reference $C$. ThenThe velocity equality follows by differentiating the hole energy with respect to ${\mathbf{k}}_h$; two minus signs cancel. The signed band effective mass is therefore opposite, becoming a positive hole mass near an electron-band maximum. The hole electric charge is $+e$ when the electron charge is $-e$. These momenta are crystal momenta, and the electron mass being compared is the signed band mass, not the bare electron mass. The positive hole current equals the current lost by removing that electron.

For a lattice-periodic one-electron Hamiltonian, Bloch's theorem givesHere $\mathbf{R}$ is any lattice translation and $n$ labels an energy band. Under that translation the wavefunction gains phase $e^{i\mathbf{k}\cdot \mathbf{R}}$. The crystal momentum $\hslash \mathbf{k}$ labels this translation eigenvalue and is defined modulo $\hslash \mathbf{G}$ for a reciprocal lattice vector $\mathbf{G}$.

The mechanical momentum is different. In zero magnetic field its operator is $-i\hslash \nabla$, which acts asA general Bloch state is therefore not a mechanical-momentum eigenstate. Expanding its periodic factor gives plane-wave components with momenta $\hslash (\mathbf{k}+\mathbf{G})$, with probabilities determined by their Fourier coefficients. For a local Hamiltonian $p^2/(2m_e)+V(\mathbf{r})$, its mean momentum satisfiesnot generally $\hslash \mathbf{k}$. The lattice exchanges actual momentum with the electron; crystal-momentum conservation in scattering is instead modulo reciprocal-lattice vectors, as in Umklapp scattering.

Use one orthonormalized localized atomic orbital $|j⟩$ at each position $ja$. In the nearest-neighbour tight-binding model, translation invariance gives the on-site energy and real hopping integralThe Bloch state isSince $H|j⟩=E_0|j⟩+t|j-1⟩+t|j+1⟩$, shifting the two summation indices givesThe hopping integral is an energy, and its sign sets whether $k=0$ is a minimum or maximum. $E_0$ is the diagonal matrix element in the crystal Hamiltonian, which can differ from an isolated-atom energy.

The orthogonal tight-binding approximation matters. If raw neighbouring orbitals retain a nonzero orbital overlap $s$ in their normalization, projection instead gives a generalized eigenvalue problem and the nonorthogonal nearest-neighbour tight-binding band $E(k)=[E_0+2h\cos (ka)]/[1+2s\cos (ka)]$. The stated cosine band follows after orthonormalization and nearest-neighbour truncation, or after neglecting that overlap metric while retaining the hopping it motivates.

A site in a primitive cubic lattice has six nearest neighbours, at $\pm a\hat{\mathbf{x}}$, $\pm a\hat{\mathbf{y}}$ and $\pm a\hat{\mathbf{z}}$. Repeating the Bloch state calculation with equal hopping integrals $t$ along all six bonds givesThe cosine sum ranges from $-3$ to $3$ within the first Brillouin zone. ThereforeFor $t<0$ the minimum is at the zone centre; for $t>0$ the maximum is there.

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.