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An electronic energy eigenstate at a fixed nuclear geometry. Its wavefunction and energy change with nuclear positions. Two same-symmetry states can exchange their dominant electronic character through an avoided crossing.

An atomic orbital is a one-electron spatial wavefunction used to describe an electron's state in a chemical atom. For a one-electron hydrogen atom, orbitals can be exact energy eigenstates; descriptions of many-electron atoms instead use an orbital approximation. A normalized atomic orbital has $\int |\varphi {|}^2{d}^3\mathbf{r}=1$, and the Born rule gives the position probability density $|\varphi {|}^2$. It is a function extending through space, not a prescribed classical orbit. ^[ref]

The linear combination of atomic orbitals combines these single-centre functions to approximate a molecular orbital. The orbital overlap measures their inner product, and their relative quantum phase controls the interference shown in molecular orbital theory.

For a normalized, smoothly chosen instantaneous energy eigenstate $|\psi (\mathbf{R})⟩$, the Berry connection has components $A_j=i⟨\psi |{\partial }_{R_j}\psi ⟩$. Its line integral around a closed parameter path $C$ gives the Berry phase in a periodic choice of state vector:Normalization makes the inner product $⟨\psi |{\partial }_{R_j}\psi ⟩$ purely imaginary, so the Berry connection is real. Changing the representative to $e^{i\chi (\mathbf{R})}|\psi ⟩$ changes the Berry connection to $A_j-{\partial }_{R_j}\chi$. A single-valued phase factor along the closed path changes the line integral by an integer multiple of $2\pi$, leaving $e^{i\gamma }$ unchanged. If the chosen vector is not periodic, include the endpoint phase:Here $\psi$ denotes the instantaneous energy eigenstate representative, with its dynamical phase removed. This is freedom to choose a representative of a state ray. ^[ref].

A Berry phase is the geometric phase acquired when a nondegenerate energy eigenstate follows a closed cycle of parameters of a Hamiltonian operator in the ideal limit of the adiabatic theorem. The energy eigenstate must stay separated from other energy eigenstates by a nonzero spectral gap, and the parameters must change sufficiently slowly. Returning the Hamiltonian operator to its starting value returns the state to the same ray, but its quantum phase can remember the journey. The total quantum phase contains both the dynamical phase and the Berry phase.

The beauty of the Berry phase is that, within the adiabatic theorem's limit, it depends on the oriented path of the parameters rather than how long the journey takes. For a spin one-half qubit, the Berry phase of a Bloch-sphere latitude turns that memory into half a solid angle. Berry-phase interference with a reference path converts this geometry into a detection probability.

Michael Berry's 1984 paper formulated the geometric phase for cycles governed by the adiabatic theorem and derived the solid angle result for spin. Its bibliographic details are Proceedings of the Royal Society of London A, volume 392, pages 45–57, DOI 10.1098/rspa.1984.0023. ^[ref]; ^[ref]. The wider concept of geometric phase does not require every cycle to obey the adiabatic theorem: Aharonov and Anandan formulated a geometric phase for general cyclic quantum evolution in 1987. ^[ref].

An isolated qubit that acquires only a global phase has unchanged measurement probabilities. To reveal the Berry phase, use two coherent paths of a Mach-Zehnder interferometer, represented by a path qubit. In one arm the internal spin one-half qubit follows the loop; in the reference arm it stays in its starting energy eigenstate. Assume equal arm amplitudes, identical final internal states, cancelled relative dynamical phases, and calibrated fixed apparatus phases. In the model above, hold the reference Hamiltonian operator at its initial value for the same duration. Both arms then have energy eigenvalue $-\Delta /2$ and acquire the same dynamical phase $\Delta T/(2\hslash )$, so their relative dynamical phase vanishes in the ideal limit of the adiabatic theorem.

The joint quantum state before recombination then factors asThe Berry phase is now a relative quantum phase between the two paths. The calibrated plus output projects onto $|+⟩=(|\mathrm{ref}⟩+|\mathrm{loop}⟩)/\sqrt{2}$. The Born rule givesFor the Berry phase of a Bloch-sphere latitude, the plus-port probabilities at $\theta =0,60^{\circ },90^{\circ },180^{\circ }$ are respectively $1,1/2,0,1$. This ideal Mach-Zehnder interferometer measurement cannot distinguish $\gamma$ from $-\gamma$ or $\gamma +2\pi$ by itself; scanning a known reference phase can resolve the sign. An uncancelled relative dynamical phase would shift the fringe as well.

The Born rule connects a quantum state to measurement probabilities. Let $\{|j⟩\}$ be a complete orthonormal basis, finite or countably infinite, for a Hilbert space, and letAn ideal measurement distinguishing these basis vectors returns label $j$ with probabilityThis assignment is a physical measurement rule. Its compatibility with total probability one follows from orthonormality and normalization:The probabilities are the squared moduli, not the amplitudes themselves or the squares $a_j^2$. ^[ref].

If the basis is an eigenbasis of an observable, the reported numerical value is its eigenvalue. Several vectors can share one eigenvalue; the probability of that value is then the sum over the corresponding basis labels. More generally, a projective measurement with orthogonal projections $P_r$ assignsfor a pure state and a general density matrix $\rho$, respectively. This also covers mixed states and degenerate eigenspaces. The Born rule determines outcome statistics; the ideal conditional state change is specified separately by the Lüders rule. See projective measurement for that formulation and its assumptions. ^[ref].

For a worked example, take the normalized qubit quantum stateThe squared moduli add to $3/4+1/4=1$. A computational-basis measurement, equivalently a measurement of the $Z$ Pauli matrix, hasThese probabilities do not depend on the relative quantum phase $\varphi$. Now choose the Hadamard basiswhose vectors are eigenstates of the $X$ Pauli matrix, also used by the Pauli X gate. The new probability amplitudes and probabilities areBoth probabilities are nonnegative and their sum is one. The relative quantum phase becomes visible because the two probability amplitudes add before their squared modulus is taken:

A Hadamard gate followed by a computational-basis measurement realizes these $X$ statistics, since $H|\pm ⟩=|0⟩,|1⟩$, respectively. Compare the two bases using fresh, identically prepared copies: a preceding measurement may change the state. The quantum superposition section shows why replacing the preparation by the mixed state $\mathrm{diag}(3/4,1/4)$ keeps the $Z$ statistics but gives $p_{+}=p_{-}=1/2$ for every $\varphi$.

The usefulness of the Born rule is this conversion from linear algebra to experimental predictions: calculate overlaps in the basis actually measured, then take squared moduli. Its appealing geometry is that changing basis redistributes probability while preserving total squared norm. The same rule relates an energy eigenstate expansion to an energy measurement and a position wavefunction to a probability density.

Born's 1926 paper on quantum scattering interpreted the outgoing-wave coefficients in terms of the probabilities of collision outcomes; a corrective footnote specified proportionality to the square of the amplitude. This is a historical scattering formulation, rather than the general density matrix formula above. ^[ref]; ^[ref].

Consider $N$ noninteracting bosons in one internal quantum state, at thermal equilibrium in the three-dimensional harmonic oscillator potentialHere $m$ is the mass, the positive ${\omega }_i$ are angular frequencies, and $\bar{\omega }$ is their geometric mean. Measure the one-particle energy $ϵ$ and chemical potential $\mu$ from the ground-state energy. The quantum harmonic oscillator levels then have $ϵ=\hslash ({\omega }_x{n}_x+{\omega }_y{n}_y+{\omega }_z{n}_z)$ with nonnegative integer $n_i$ and reduced Planck constant $\hslash =h/(2\pi )$.

When $ϵ\gg \hslash {\omega }_i$, counting lattice points can be approximated by the volume of a tetrahedron in the positive octant of $(n_x,n_y,n_z)$:This is a density of states, with units of inverse energy. The factor $1/6$ is the unit tetrahedron volume; differentiating produces the factor $1/2$. Treat the single ground state separately: its macroscopic population would be lost by replacing every level with a smooth density of states.

For $k_{B}T\gg \hslash {\omega }_i$, integrate the Bose-Einstein distribution over excited energy eigenstates. As $\mu$ approaches zero from below, their maximum population isHere $k_B$ is the Boltzmann constant and $\zeta$ the Riemann zeta function. A short proof uses $1/(e^x-1)={\sum }_{\ell \ge 1}{e}^{-\ell x}$ and ${\int }_0^{\infty }{x}^2{e}^{-\ell x}dx=2/{\ell }^3$. The nonnegative terms permit exchanging summation and integration by Tonelli's theorem, giving ${\int }_0^{\infty }{x}^2/(e^x-1)dx=2\zeta (3)$. Near zero the integrand is proportional to $x$, so its integral converges. That finite excited-state capacity is the mechanism of Bose-Einstein condensation.

Set $N_{\mathrm{ex}}^{\mathrm{sat}}(T_c)=N$. Particle conservation gives, to this continuum accuracy,Above $T_c$, the macroscopic condensate fraction is zero and the chemical potential adjusts below zero. This cubic power belongs to a three-dimensional harmonic trap; it is not the homogeneous three-dimensional ideal gas exponent. For $N=10^5$, $\bar{\omega }/(2\pi )=100\mathrm{Hz}$ and $\zeta (3)\simeq 1.202056903$, the model gives $T_c\simeq 209.5\mathrm{nK}$. At $T=0.8T_c\simeq 167.6\mathrm{nK}$, $N_0/N=0.488$, or approximately $48800$ condensed bosons. These are chosen parameters and calculated values.

Finite $N$ gives a smooth crossover rather than a sharp phase transition. The exact ideal gas sum over excited quantum harmonic oscillator levels differs from the continuum integral, especially when $k_{B}T$ is not large relative to every $\hslash {\omega }_i$. A sharp trapped-gas limit takes $N\to \infty$, $\bar{\omega }\to 0$ with $N{\bar{\omega }}^3$ fixed and fixed frequency ratios. Interactions also alter the critical temperature, condensate fraction and release profile; a dilute gas can have appreciable interaction energy compared with the trap level spacing. The cubic law is a useful baseline, not a fit guaranteed for either 1995 experiment.

For a normalized sufficiently regular solution of the Schrödinger equation on $[0,L]$ with Dirichlet walls, the instantaneous outward forces on the walls have magnitudesA wall displacement changes the kinetic-energy quadratic form by the boundary term $-P_{j}d{L}_j$, giving the local force. Equivalently, direct integration by parts in the time derivative of the mean particle momentum givesThe force on the particle is the opposite of the net force $-P_0+P_L$ on the walls. For a stationary energy eigenstate each magnitude equals $2E_n/L$. For the equal superposition of the first two box states, writing $C=E_1/L$ and $\Omega =3E_1/\hslash$ gives $P_0=C(5+4\cos \Omega t)$ and $P_L=C(5-4\cos \Omega t)$. Both time averages equal $2⟨E⟩/L$, the classical mean force on one wall at that energy, even though the quantum forces vary continuously in time.

The canonical ensemble is the probability distribution for a system in thermal equilibrium with a heat bath at fixed temperature $T$, with fixed particle number and external parameters. It allows energy exchange, so individual energy measurements fluctuate. With Boltzmann constant $k_B$ and inverse temperature $\beta =1/(k_{B}T)$,The heat bath is idealized as large enough that exchanges barely change its temperature; coupling must permit equilibration while contributing negligible interaction energy. A finite heat bath approximates this description only when its temperature change is negligible over the relevant exchanges. Strong coupling or a small heat bath can require a different description.

For one two-level system at positive temperature, the Boltzmann weights are $1,e^{-\beta \Delta }$, henceAt $\beta \Delta =\ln 3$, $Z_1=4/3$ and $p=1/4$. This is a probabilistic thermal mixed state. For quantum levels, its density matrix is $\rho =(1-p)|0⟩⟨0|+p|1⟩⟨1|$. The pure state $\sqrt{1-p}|0⟩+\sqrt{p}|1⟩$ has the same energy measurement probabilities, but also has quantum coherence between the energy eigenstates. Matching those probabilities does not make the states equivalent.

The partition function $Z(\beta )={\sum }_s{e}^{-\beta E_s}$ is the sum of the Boltzmann weights over individual microstates. Dividing by it makes their probabilities sum to one. When summing distinct energies instead, include the state degeneracy: $Z={\sum }_{E}g(E)e^{-\beta E}$. For two independent distinguishable two-level systems,The middle coefficient counts two microstates, exactly as in the preceding figure. For $N$ such units, $Z_N=Z_1^N$; this factorization requires additive energy and independence, and generally fails with interactions.

The usefulness goes beyond normalization. For fixed energies, derivatives of the natural logarithm of the partition function yield measurable quantities:Here $U$ is internal energy, the second expression is the energy variance, and $S$ is Gibbs entropy. For one two-level system at fixed $\Delta$, its heat capacity $C=\partial U/\partial T$ and entropy areAt $\beta \Delta =\ln 3$, these give $U/\Delta =0.25$, $C/k_B\simeq 0.2263$ and $S/k_B\simeq 0.5623$. For independent units, all three quantities add.

The figure shows why heat capacity peaks. At low temperature, the excited energy is rarely occupied; at high temperature, the probabilities are almost equal and further warming barely changes internal energy. The largest response lies between these limits, at $k_{B}T/\Delta \simeq 0.4168$, where $C/k_B\simeq 0.4392$. Meanwhile entropy rises from zero toward $k_B\ln 2$, reflecting two equally likely alternatives. This high-temperature limit belongs to the stipulated two-level system; extra accessible energy eigenstates would change it.

In the isotropic three-dimensional quantum harmonic oscillator, the first excited Cartesian energy eigenstates are proportional to $x,y,z$ times the common Gaussian $e^{-r^2/(2a_0^2)}$. If ${\varphi }_x,{\varphi }_y,{\varphi }_z$ are normalized with the same real phase convention, their combinations in the title are normalized angular momentum eigenstates with $l=1$ and $m=1,0,-1$.

Indeed, $z=r\cos \theta$ and $x\pm iy=r\sin \theta e^{\pm i\phi }$ identify a common radial factor times the spherical harmonics $Y_{10},Y_{1,\pm 1}$. The transformation is unitary, so it changes the basis rather than the threefold orbital degeneracy.

A Chern insulator is a two-dimensional band insulator whose occupied energy bands have a nonzero total Chern number. It has a bulk band gap, yet an interface with a topologically trivial band insulator carries a net excess of quantum Hall edge states propagating in one direction. Time-reversal symmetry must be broken. The Haldane model shows that a nonzero average magnetic flux is unnecessary.

Why distinguish two solids that both have a band gap? The energy eigenvalues tell us whether an excitation costs energy; the energy eigenstates also describe how the state changes around the Brillouin zone. Their Berry curvature can integrate to a nonzero integer. A small deformation changes the Berry curvature continuously, but cannot continuously change an integer. A Chern insulator and a trivial band insulator therefore cannot be connected through a path of isolated occupied energy bands with a common bulk band gap. The distinction survives sufficiently weak local perturbations. It does not make every microscopic quantity or every boundary state immune to every disturbance.

For a single filled energy band, set the Berry connection to ${\mathcal{A}}_j=i⟨u_{-}|{\partial }_{k_j}{u}_{-}⟩$, and orient the momentum plane by $(k_x,k_y)$. ThenThis is the First Chern class evaluated on the Brillouin zone, a torus. Smooth eigenvectors may require multiple patches; their transition phases have integer winding numbers. For charge $-e$ and conventional electric current $j_i={\sigma }_{ij}{E}_j$, these conventions give ${\sigma }_{yx}=C{e}^2/h$ and ${\sigma }_{xy}=-C{e}^2/h$. The measurable magnitude agrees with Chern number and integer Hall conductivity. Reversing the momentum orientation or the sign of the Berry connection reverses the displayed $C$.

For $\mathbf{d}\ne 0$, put $\hat{\mathbf{d}}=\mathbf{d}/|\mathbf{d}|$. The lower-band orthogonal projector is $P_{-}=(I-\hat{\mathbf{d}}\cdot \mathbf{\sigma })/2$. Applying the Pauli matrix multiplication law to $i\mathrm{Tr}(P_{-}[{\partial }_{k_x}{P}_{-},{\partial }_{k_y}{P}_{-}])$ givesThus the Chern number is the signed number of times the Brillouin zone covers a two-sphere under $\hat{\mathbf{d}}$. The lower energy eigenstate's actual Bloch vector is $-\hat{\mathbf{d}}$. The Berry curvature has the displayed positive sign for this lower band and the stated Berry connection; switching to the upper band changes its sign.

A useful local calculation exposes what each valley contributes. Write $p=\hslash v|\mathbf{q}|$. The linear Dirac Hamiltonian givesEach unbounded continuum cone gives a half-integer in this calculation. It is not a separately realizable half-integer Chern number of an isolated lattice energy band. The full honeycomb lattice supplies both valleys and the large-momentum completion. Starting with a trivial large-$|M|$ state, each single-valley mass crossing changes the lattice integer by the corresponding unit. There are no other band touchings. This establishes the exact lattice resultfor $t_2>0$, excluding the boundaries. This sign belongs to our explicit bond vectors, orientation and occupied-band convention.

For an original worked example, choose $t_1=1$, $t_2=0.08$, $\varphi =\pi /2$ and $M=0$. Then $\mu \simeq 0.415692$, $(m_{+},m_{-})=(-\mu ,+\mu )$, both valley gaps are $2\mu \simeq 0.831384$, and $C=-1$. Choosing instead $t_2=0$, $M=\mu$ gives exactly the same valley-gap magnitudes but $C=0$. The first state's two valley contributions reinforce; the second state's cancel.

An independent eigenvector-overlap calculation on periodic $31\times 31$, $61\times 61$ and $121\times 121$ momentum grids gives $C=-1$ for the first example and $C=0$ for the second. Reversing $\varphi$ in the first example gives $C=+1$. Direct integration of the analytic lattice Berry curvature agrees. For the overlap calculation one can remove the embedding phase from $f$, replacing it by $1+e^{i\mathbf{k}\cdot {\mathbf{a}}_1}+e^{i\mathbf{k}\cdot {\mathbf{a}}_2}$; this makes the cell-basis Hamiltonian periodic and prevents a false boundary-seam contribution. The local Berry curvature can depend on this basis convention; the integrated Chern number agrees. All mass-zero parameters are excluded before evaluating any integer.

Suddenly shifting a quantum harmonic oscillator equilibrium from zero to a signed position $x_0$ leaves the old ground state unchanged at the instant of the quantum quench. The new annihilation operator is $a^{\prime }=a-\lambda$, with $\lambda =\sqrt{m\omega /(2\hslash )}{x}_0$, so $a^{\prime }|0⟩=-\lambda |0⟩$. In the translated energy eigenstates $|n^{\prime }⟩=e^{-ip{x}_0/\hslash }|n⟩$, the expansion isThe sign follows by translating the old vacuum by $-x_0$ before expanding it in the old Fock states. A Baker--Campbell--Hausdorff formula with central commutator separates the resulting exponential into creation and annihilation parts. Evolution with the shifted Hamiltonian preserves this coherent state, with $\alpha (t)={\alpha }_0{e}^{-i\omega t}$. Its mean occupation is $|{\alpha }_0{|}^2$ and its mean energy above the new potential minimum is $\hslash \omega (|{\alpha }_0{|}^2+1/2)$. Omitting $(-\lambda {)}^n$ in favour of $|\lambda {|}^n$ changes the state when $x_0>0$.

Choose the one-particle states of a hydrogen atom, or a central-field description of a chemical atom, with labelsThe principal quantum number $n$ identifies the electron shell. The orbital angular momentum label $\ell$ identifies the electron subshell; the magnetic quantum number $m_{\ell }$ labels $2\ell +1$ independent spatial orbitals. Each has two spin one-half along an axis choices, hence $2(2\ell +1)$ spin orbitals. Applying the Pauli exclusion principle once per spin orbital givesThese quantum numbers label wavefunctions and spin projections, not electron trajectories. They need not resolve exact energy eigenstates in the presence of spin-orbit interaction; changing to coupled angular momentum eigenstates preserves the count of independent one-particle states within this shell model.

For example, $n=3$ allows $\ell =0,1,2$, conventionally $3s,3p,3d$. Their spatial orbital counts are $1,3,5$; their spin orbital counts are $2,6,10$. The sum is eighteen. The algebra behind “one per complete state” is short: two-particle antisymmetrization gives $u\wedge u=(u\otimes u-u\otimes u)/\sqrt{2}=0$, and the zero vector cannot be a normalized quantum state. Opposite-spin electrons in the same spatial orbital have distinct complete states, so their antisymmetric product survives.

This supplies a structural link to the periodic table: finite electron subshell capacities make repeated patterns of occupied electron configurations possible. It does not predict the exact ground state electron configuration or energy of a many-electron chemical atom. Different electron subshells overlap in energy, and electron interactions change their ordering. In particular, the periodic table period lengths are not simply successive $2n^2$ values: the third periodic table period has eight chemical elements, although the full $n=3$ electron shell has eighteen available states. A capacity counts available spin orbitals; an actual filling order requires a Quantum Hamiltonian.

A diagonal Hamiltonian is diagonal in a specified product basis, usually the computational basis. Every basis state is therefore an energy eigenstate, and optimization of its diagonal entries becomes minimization of the corresponding classical cost function.

In a dilute gas, Bose-Einstein condensation makes a single one-particle state hold a substantial fraction of the bosons. This is a population effect: cooling reduces the number that the excited energy eigenstates can accommodate at thermal equilibrium. The surplus accumulates in a Bose-Einstein condensate. For an ideal gas the occupied mode is the trap ground state; interactions can deform that mode, as described by the Gross–Pitaevskii equation. Dilute does not mean classical: a small number density can still give overlapping thermal de Broglie wavelengths at sufficiently low temperature.

The appeal is that changing the trap changes a calculable Quantum Hamiltonian, while absorption imaging makes its population distribution visible. The Bose condensation in a three-dimensional harmonic trap below turns density of states into a prediction for a critical temperature and condensate fraction. These are separate questions from measuring matter-wave coherence or superfluidity.

Eric A. Cornell and Carl E. Wieman's joint lecture emphasizes the competition between useful elastic collisions, which restore thermal equilibrium during evaporative cooling, and collisions that remove or heat the trapped sample. A long trap lifetime alone is insufficient: reequilibration must keep up with evaporation.^[ref]

For an energy eigenstate with instantaneous energy eigenvalue $E(t)$, the dynamical phase isIt comes from the Schrödinger equation and depends on the time spent evolving. In an ideal cycle under the adiabatic theorem, a periodic choice of instantaneous energy eigenstate gives $|\Psi (T)⟩=e^{i(\delta +\gamma )}|\Psi (0)⟩$, with Berry phase $\gamma$.

A change between electronic energy eigenstates of a chemical atom or another system.

A nonzero position-space wavefunction representing an energy eigenstate. For a time-independent Quantum Hamiltonian, its time evolution is a global phase, so its position probability density is stationary.