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Reordering an orthonormal basis changes its matrix by a permutation similarity transformation. The off-diagonal block can move to different row and column indices without changing any energy eigenvalue. Matrix entries must therefore be compared in the same declared basis order, not only by their visual positions.

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.

Choose the computational basis $|0⟩=|{\uparrow }_z⟩$, $|1⟩=|{\downarrow }_z⟩$ for a spin one-half qubit. On the Bloch sphere, let $\mathbf{n}=(\sin \theta \cos \varphi ,\sin \theta \sin \varphi ,\cos \theta )$ and use the normalized quantum stateThis is the $+1$ eigenstate of $\mathbf{n}\cdot \mathbf{\sigma }$, where $\mathbf{\sigma }$ are the Pauli matrices. To make it an instantaneous ground state, take the model Hamiltonian operator $H=-\Delta \mathbf{n}\cdot \mathbf{\sigma }/2$ with constant $\Delta >0$. Its energy eigenvalues are $-\Delta /2$ and $+\Delta /2$, so its spectral gap is $\Delta$ everywhere. The spin points along $\mathbf{n}$; this explicit convention fixes the sign of the Berry phase.

Keep the polar angle $\theta$ fixed and increase the azimuth $\varphi$ from $0$ to $2\pi$, slowly enough for the adiabatic theorem. The state vector written above is periodic in $\varphi$. Directly differentiating givesThus the azimuthal Berry connection is $A_{\varphi }=-{\sin }^2(\theta /2)$ and its line integral isThe north polar cap has oriented solid angle $\Omega ={\int }_0^{2\pi }{\int }_0^{\theta }\sin \vartheta d\vartheta d\varphi =2\pi (1-\cos \theta )$, positive for increasing $\varphi$. Reversing the loop reverses the Berry phase. The opposite spin eigenstate has the opposite Berry phase modulo $2\pi$.

At $\theta =60^{\circ }$, the solid angle is $\pi$ and the Berry phase is $-\pi /2$. At $\theta =90^{\circ }$, the solid angle is $2\pi$ and the Berry phase is $-\pi$. At $\theta =0$, the loop collapses and $\gamma =0$. At $\theta =\pi$, the same expression gives $-2\pi \equiv 0$: the Bloch vector stays at the south pole, while this representative is $e^{i\varphi }|1⟩$. Its winding is only a choice of global phase, so the physically relevant phase factor is again one. The displayed formula is a continuous, unwrapped representative, not a unique real-valued observable.

Real chemical bonds can stretch as molecular rotation increases. The resulting larger moment of inertia lowers the energy eigenvalues relative to a rigid rotor. Within one vibrational quantum state, a leading effective correction isBoth $B_v$ and $D_v$ are in frequency units here; $v$ labels the vibrational quantum state. For positive $D_v$, the adjacent-line spacing becomesso the departures grow with $J$. Molecular vibration also changes the effective rotational constant: even the lowest vibrational quantum state does not have motionless atomic nuclei.^[ref]

The quartic correction is a limited expansion, not a model to extrapolate to arbitrary $J$. It is small relative to the rigid contribution only while $(D_v/B_v)J(J+1)\ll 1$; eventually higher terms, changed internal motion, or chemical bond breaking matter. In the synthetic plot, the largest upper-state label is $J=5$, giving a stipulated correction ratio of $0.03$. No universal maximum valid $J$ follows without a particular molecule and precision target.

The quantum numbers also have limits of meaning. Here $J$ describes spin-free rotation. In a molecule with electronic spin, rotation alone is commonly labelled $N$, while $J$ includes electronic angular momentum; including nuclear spin introduces additional total-angular momentum labels and resolved splittings. An applied electric field can mix different field-free $J$ states through the Stark effect. For identical atomic nuclei, the Pauli exclusion principle can restrict combinations of rotational and nuclear-spin states. The simple $2J+1$ degeneracy and every-integer-$J$ ladder therefore describe the stated idealization, not all observed sublevels.^[ref]

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 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 $\gamma$.

The Einstein model of a solid represents the vibrations of $N$ chemical atoms by $3N$ independent one-dimensional quantum harmonic oscillators, all with the same positive angular frequency $\omega$. Equivalently, each chemical atom has three independent oscillator directions. The common angular frequency is a simplifying model assumption, not a claim about every vibration of a real solid. Hold the volume, $N$ and $\omega$ fixed. Define the characteristic temperature ${\theta }_E=\hslash \omega /k_B$ and the dimensionless ratio $x={\theta }_E/T$. The vibrational internal energy isThe first term is the zero-point energy $3N\hslash \omega /2$. It is constant at fixed $\omega$, so it contributes no heat capacity at constant volume. The temperature-dependent term givesThis is the vibrational heat capacity at constant volume of the model, with no expansion or other contributions included. ^[ref]

For a worked comparison, choose the model parameter ${\theta }_E=300\mathrm{K}$. The normalized heat capacity at constant volume depends only on $T/{\theta }_E$:

At $T={\theta }_E$, one mole of chemical atoms therefore has vibrational heat capacity at constant volume $3R(0.92067)\simeq 22.965\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-1}$, using the unrounded model value. Even at twice the characteristic temperature, the model remains about $2.06\%$ below the Dulong-Petit law limit. These are calculations for the ideal Einstein solid, not material measurements.

A short derivation uses the thermal partition function of a quantum harmonic oscillator. The energy eigenvalues $E_n=\hslash \omega (n+1/2)$ and their Boltzmann factors form a geometric series, giving the one-oscillator canonical partition function $z=e^{-x/2}/(1-e^{-x})$. The mean occupation is $1/(e^x-1)$, hence the displayed $U$ after summing over $3N$ independent quantum harmonic oscillators. Taking its derivative with $dx/dT=-x/T$ gives the displayed heat capacity at constant volume. ^[ref]

The two limits explain the shape. At high temperature, a Taylor series in small $x$ givesAt low temperature, $1-e^{-x}\to 1$, soThe zero-point energy remains even when the thermal response is tiny: freeze-out means that changing temperature scarcely changes the occupations, not that the chemical atoms have zero energy. This is the useful lesson of the Einstein model of a solid: the classical counting rule reappears when many levels are accessible, while discrete excitation spacings explain its failure upon cooling.

The exponential low-temperature decay is also the model's limitation. Real three-dimensional crystalline solids have acoustic phonon branches with arbitrarily small angular frequencies in the bulk limit. The Debye model includes these collective normal modes and predicts a low-temperature vibrational contribution $C_V\propto T^3$, which the single-frequency Einstein solid cannot reproduce. This qualification concerns the vibrational contribution; additional excitations can change a material's total heat capacity. ^[ref]

Einstein introduced the quantum treatment of solid vibrations in his 1907 paper Die Plancksche Theorie der Strahlung und die Theorie der spezifischen Wärme. Its historical importance is that quantum excitation energies explained why the classical Dulong-Petit law could fail; the modern quantum harmonic oscillator formulation above includes the zero-point energy explicitly. ^[ref]

The energy eigenspace at $E$ is the vector subspacewhere $H$ is the Hamiltonian operator and $I$ is the identity operator. It is nonzero exactly when $E$ is an energy eigenvalue. Its dimension is the multiplicity of that energy eigenvalue; degenerate energy levels have multiplicity greater than one. The ground-state subspace is ${\mathcal{E}}_{E_0}$, and its dimension is the ground-state degeneracy. A vector in an energy eigenspace need not be one of a specially chosen orthonormal basis of energy eigenstates.

Linearity makes the useful point immediate: if $H{\varphi }_1=E{\varphi }_1$ and $H{\varphi }_2=E{\varphi }_2$, then $H(a{\varphi }_1+b{\varphi }_2)=E(a{\varphi }_1+b{\varphi }_2)$. Every normalized nonzero combination stays in the same energy eigenspace. For a time-independent Hamiltonian operator, its evolution is multiplication by the common global phase $e^{-iEt/\hslash }$, so it is a stationary state. A quantum superposition within a degenerate energy eigenspace can change spatial shape when its coefficients are chosen differently, but its density does not subsequently beat under this unchanged Hamiltonian operator.

Across distinct energy eigenspaces, relative quantum phases evolve. For orthonormal eigenfunctions ${\varphi }_1,{\varphi }_2$ of the Hamiltonian operator with energy eigenvalues $E_1\ne E_2$, an equal-weight quantum superposition hasand position probability densityThe interference term can change local probabilities even though the Born rule assigns the same time-independent probability $1/2$ to each energy measurement outcome. Orthogonality makes its integral zero, preserving wavefunction normalization. This pure state is not a stationary state; some particular measurement distributions may nevertheless remain constant. An incoherent mixed state with the same energy populations has no such interference term.

For the pictured infinite square well, $\theta =3E_{1}t/\hslash$ and the interference repeats after $T=2\pi \hslash /(3E_1)$. At $t=0$, direct integration gives $⟨x⟩=L/2-16L/(9{\pi }^2)$; halfway through the period it is $L/2+16L/(9{\pi }^2)$. This is a moving expectation value, rather than a trajectory of an individual particle. The distinction between an energy eigenspace and a combination of different energy eigenspaces is what makes the different behavior possible.

An energy eigenstate is a quantum state represented by an eigenvector of the Quantum Hamiltonian. For a time-independent Quantum Hamiltonian, a normalized eigenfunction $\varphi$ with energy eigenvalue $E$ evolves according to the Schrödinger equation asHere $\hslash =h/(2\pi )$ is the reduced Planck constant. The changing factor is a global phase, so this is a stationary state: its position probability density is constant. For example, the second infinite square well mode has two density lobes separated by a node of a standing wave at $x=L/2$; both lobes stay fixed while its quantum phase rotates. An ideal energy measurement returns $E$ with probability one, but a position measurement still has a distribution. Stationary density does not describe a particle sitting at the peak of a lobe. Distinct energy eigenvalues accumulate different quantum phases, making their quantum superposition behave differently.

An energy eigenvalue is an eigenvalue of the Hamiltonian operator $H$: there is a nonzero vector $\psi$ in its operator domain $D(H)$ withFor a self-adjoint operator, $E$ is real. Normalizing $\psi$ produces an energy eigenstate; an ideal energy measurement then returns $E$ with probability one. The associated energy eigenspace includes all vectors with this same energy eigenvalue, including the zero vector, which represents no quantum state. Different energy eigenvalues have orthogonal energy eigenspaces. ^[ref].

The energy eigenvalues form the point spectrum, which can be only part of the spectrum. The term discrete spectrum more specifically means isolated eigenvalues of finite multiplicity. The usual fixed-nucleus hydrogen atom model has discrete negative bound state energy eigenvalues together with a continuum at nonnegative energy. ^[ref]. A quantum system need not have a ladder of discrete energy eigenvalues: a whole-line free particle has continuous spectrum. A plane wave used for a free particle is a generalized eigenfunction of the Hamiltonian operator, rather than a normalized vector in the physical Hilbert space. ^[ref].

For the infinite square well $0<x<L$, the Dirichlet boundary conditions giveSubstitution into $H{\varphi }_n=E_n{\varphi }_n$ and wavefunction normalization verify these statements directly. Here $E_1$ is the ground-state energy, even though its index is one; the labeling convention does not determine which quantum state is lowest. Equal populations of ${\varphi }_1$ and ${\varphi }_2$ have energy expectation value $(E_1+E_2)/2=5E_1/2$, but an energy measurement returns $E_1$ or $4E_1$, each with probability $1/2$. An average of allowed energy eigenvalues need not itself be an energy eigenvalue.

The number of independent quantum states sharing one energy eigenvalue. A level of angular momentum $J$ has $2J+1$ magnetic substates when no interaction splits them.

Suppose a constant Hamiltonian operator has a complete discrete orthonormal basis of energy eigenstates, $H|n⟩=E_n|n⟩$. Expanding an initial pure state and applying the time-evolution operator term by term givesA projective measurement resolving these basis vectors therefore assigns the same Born rule probability $|c_n{|}^2$ to each label $n$ at every time. An energy measurement groups labels sharing the same energy eigenvalue: $P(E)={\sum }_{n:E_n=E}|c_n{|}^2$ is also constant. If $c_m,c_n\ne 0$, their probability amplitude ratio instead evolves asOnly energy differences enter this relative quantum phase. Adding a constant $\epsilon I$ to the Hamiltonian operator multiplies the entire pure state by $e^{-i\epsilon t/\hslash }$, a global phase, and leaves the density operator unchanged.

For a fixed observable $A$, the expectation value can nevertheless vary:Terms joining distinct energy eigenvalues can oscillate; diagonal terms cannot. If $[A,H]=0$, these terms between different energies vanish, so the expectation value is constant. This distinguishes conservation of energy from the stronger claim that every observable is stationary.

An energy eigenstate has only a global phase evolution and is a stationary state. A quantum superposition entirely within one degenerate energy eigenspace is also an energy eigenstate and is stationary. For a general density operator in finite dimension, stationarity under a constant Hamiltonian operator means $[H,\rho ]=0$: differentiating $U\rho U^{†}$ proves necessity, and commuting $\rho$ through the exponential proves sufficiency. Merely fixing the diagonal energy populations does not fix the off-diagonal quantum coherence.

A physicist who developed wave mechanics. In 1926, Erwin Schrödinger made the energies of chemical atoms an eigenvalue problem, rather than prescribing a separate quantization rule for each classical orbit. He shared the Nobel Prize in Physics in 1933 with Paul Dirac.^[ref]

The Schrödinger equation turns a proposed Hamiltonian operator into predictions for a wavefunction and its evolution. Boundary conditions can select discrete energy eigenvalues, while quantum superposition makes their relative quantum phases observable through interference. The infinite square well gives a transparent worked example; a hydrogen atom supplies a physical application with a different potential energy.

The Davisson–Germer experiment gives a complementary experimental route into matter waves: an accelerated electron beam scattered from a nickel crystal produces direction-dependent collected electric current. Its apparatus and angular scans make the wave prediction testable. Interpreting a wavefunction as a probability amplitude also requires the Born rule; that statistical interpretation deserves its own history alongside Erwin Schrödinger's dynamics.

In the stationary-state terminology used here, an excited state is a normalized energy eigenstate with energy eigenvalue $E>E_0$, where $E_0$ is an attained ground-state energy. Its excitation cost above the ground state is $\Delta E=E-E_0>0$. Several energy eigenstates can share one excited energy eigenvalue through degenerate energy levels. An arbitrary quantum superposition with energy expectation value above $E_0$ need not be a single stationary excited state; its energy content is described by its Born rule probabilities or, for a continuum, its scalar spectral measure.

An excited state can be a stationary state: the second infinite square well mode is an immediate example. Spontaneous photon emission is a transition caused by coupling matter to the electromagnetic field; it is absent from an isolated matter-only Hamiltonian operator. The relevant energy eigenstate of that isolated model is therefore not automatically an energy eigenstate of the full interacting system. This distinction explains how an ideal stationary excited state can approximate a state with a finite experimental lifetime. See electric-dipole interaction for the coupling used in the simplest optical model.

For a one-photon transition between stationary internal states, neglecting recoil, conservation of energy requiresHere $h$ is the Planck constant and $\nu$ is the photon frequency. Energy matching alone does not guarantee a transition: in the electric-dipole interaction approximation its strength also involves the matrix element $⟨f|\mathbf{d}\cdot \mathbf{ϵ}|i⟩$, where $\mathbf{d}$ is the electric dipole moment operator and $\mathbf{ϵ}$ specifies photon polarization. A zero matrix element gives an electric-dipole selection rule. Thus an absent optical line does not prove the corresponding energy eigenvalue is absent; a different interaction can couple different states. ^[ref]. The Franck-Hertz experiment gives a particularly instructive comparison between collision excitation and photon emission.

The first excited state terminology assumes a least energy eigenvalue above $E_0$. Such a next level is not guaranteed by quantum mechanics: a continuous spectrum can start immediately above the spectral bottom, or energy eigenvalues can accumulate there. For example, a Hamiltonian operator with energy eigenvalues $0,\epsilon ,\epsilon /2,\epsilon /3,\dots$, where $\epsilon >0$, has a ground-state energy zero but no least positive energy eigenvalue: every candidate $\epsilon /n$ is exceeded downward by $\epsilon /(n+1)$. A free particle on the whole line has neither a ground state nor a first stationary excited state. Each use of a discrete excitation ladder therefore needs a specified Hamiltonian operator and its boundary conditions.

The exciton binding energy is the positive energy needed to separate a bound electron and electron hole into the relevant unbound scattering states. Compare the exciton energy $E_X$ with the continuum threshold $E_{\mathrm{cont}}$ at the same total crystal momentum and for the same energy bands. The negative internal energy eigenvalue $-E_B$ and the positive separation cost $E_B$ are different sign conventions for related quantities. An exciton may move freely through a perfect crystal while remaining internally bound: “free exciton” does not mean an unbound pair.

For the ideal Wannier-Mott exciton in energy bands whose edges occur at the same crystal momentum, the pair excitation energy, measured from the unexcited crystal, isHere $\hslash \mathbf{K}$ is the pair's total crystal momentum; the last term is center of mass kinetic energy. For a permitted photon absorption transition with negligible recoil energy, $\hslash \omega \simeq E_g-E_{B,n}$. An electric-dipole selection rule and a nonzero transition matrix element are still needed: a bound state need not produce an observable spectral line. If the relevant energy band edges have different values of crystal momentum, a phonon can also be needed to conserve crystal momentum; subtracting a binding scale from a band gap alone does not specify the optical threshold.

For example, the lowest internal bound state in this hypothetical model costs $1.489115\mathrm{eV}$ to create optically, yet needs only $0.010885\mathrm{eV}$ more to dissociate. The large creation energy and the small exciton binding energy answer different physical questions. An electron-hole recombination event can instead release excitation energy by photon emission or to other degrees of freedom; an emitted photon need not reproduce the original absorption energy if relaxation intervened.

For finitely many microstates with finite energies $E_{\alpha }(h)$ that are real analytic functions of a real control $h$, the canonical partition function at $T>0$ is a finite positive sum:It and the resulting Helmholtz free energy are locally real analytic functions of $T$ and $h$. Hence such a finite Ising model has no literal nonanalytic equilibrium phase transition. A limit of these real analytic functions can nevertheless fail to be a real analytic function; the narrow but smooth crossover can become a sharp phase transition.^[ref]

Finite particle number alone is not the hypothesis of a finite sum. Classical phase space is continuous, and a system of quantum states can have infinitely many energy eigenvalues: its partition function requires convergence and local bounds that permit differentiation or an analytic extension of the integral or thermal trace. A divergent partition function, a singularly changed statistical Hamiltonian, or the zero-temperature limit falls outside the finite-positive-sum argument. Observing a steep change in a finite sample therefore motivates a limiting model; it does not measure an actual infinity.

The Franck-Hertz experiment connects a reproducible loss of electron kinetic energy with excitation of a chemical atom. The original mercury-vapor experiments were performed during 1912–1914 while investigating ionization; they were not designed as a test of the Bohr model. Their later interpretation distinguished internal excitation from removal of an electron. ^[ref].

In a modern mercury tube, a heated cathode emits electrons and a positive perforated grid accelerates them through Hg vapor. A collector slightly below the grid's electric potential rejects slow electrons. The oven controls vapor density and hence the mean free path. Keep heating and retarding settings fixed, sweep the accelerating electric potential difference $V$, and record collector electric current $I(V)$. These measured quantities indirectly probe atomic excitation. ^[ref].

The curve shows repeated current minima, typically about $4.9\mathrm{V}$ apart. In the collision model, an electron gains approximately $eV$ of kinetic energy, with $e$ the positive elementary charge. An inelastic collision transfers about $4.9\mathrm{eV}$ to internal excitation. Near the grid, this can prevent the electron crossing the retarding region, lowering collected electric current. Further acceleration restores collection; repeated excitation losses produce further minima. These represent multiple collisions, rather than equally spaced atomic energy eigenvalues. Contact potentials shift the first minimum, so compare several successive spacings instead of identifying the first dip's voltage with the excitation cost. ^[ref].

The optical comparison supplies a second observable: mercury radiation at a wavelength near $253.6\mathrm{nm}$ was detected through a window in the tube. Its inferred photon energy $hc/\lambda \approx 4.89\mathrm{eV}$ agrees with the characteristic collision loss, with $c$ the speed of light. This agreement supports the interpretation as a transition between internal atomic energies. It does not make the collector trace a complete spectrum. In particular, the lowest excited mercury level, labeled $6{}^3{P}_0$, is metastable because an electric-dipole selection rule forbids its direct transition to the ground state; the nearby $6{}^3{P}_1$ level emits the quoted ultraviolet line. Collision excitation and optical detection therefore have different sensitivities to the available excited states. ^[ref].

Initial electron kinetic energy spread and varying collision positions broaden real minima. Repeat traces at different retarding settings and oven temperatures to distinguish excitation from collection effects. This probes a discrete energy-transfer channel, rather than every energy eigenspace, its dimension, or an absolute ground-state energy. ^[ref].

James Franck and Gustav Ludwig Hertz presented their paper on 24 April 1914. Its heated platinum wire sat inside a cylindrical platinum mesh, with a collector 1–2 mm beyond it. A heated bath and pumping prepared the vapor; guard rings suppressed leakage. They differentiated retarding-electric current scans to study outgoing energies.^[ref]

Their 1925 Nobel Prize preceded their lectures of 11 December 1926. James Franck described choosing pressure for many collisions before the mesh but few afterward.^[ref] Gustav Ludwig Hertz explained how a field-free collision region narrowed excitation thresholds.^[ref]

For a particle on a circle with arc length $x\sim x+2\pi R$ and periodic boundary conditions, the Hamiltonian operator $P^2/(2m)$ has orthonormal basis ${\varphi }_n=e^{inx/R}/\sqrt{2\pi R}$, $n\in \mathbb{Z}$, and energy eigenvalues $E_n={\hslash }^2{n}^2/(2m{R}^2)$. To see this, periodicity forces the wave number to be $n/R$, and applying the momentum operator $-i\hslash {\partial }_x$ gives $\hslash n/R$. The integral of $|{\varphi }_n{|}^2$ over one turn is one. The zero energy eigenvalue is simple; each positive energy eigenvalue has quantum degeneracy two, from $n$ and $-n$.

A ground state is a normalized energy eigenstate that attains the lowest possible energy of a quantum system. Precisely, let the Hamiltonian operator $H$ be a self-adjoint operator bounded below on a Hilbert space, and write $E_{\ast }=\inf \sigma (H)$ for the infimum of its spectrum. A ground state is a unit vector ${\psi }_0$ in the operator domain $D(H)$ satisfyingThus a ground state exists exactly when the spectral bottom $E_{\ast }$ is an energy eigenvalue. The lowest energy eigenvalue among some listed bound states is insufficient if other parts of the spectrum lie below it. The ground-state subspace collects all minimizing energy eigenstates; it can have ground-state degeneracy. The quantum variational principle characterizes $E_{\ast }$ as the infimum of normalized energy expectation values. ^[ref].

For the one-dimensional quantum harmonic oscillator, the ground state has energy $\hslash \omega /2$ above the minimum of the potential energy. This zero-point energy is compatible with being the lowest allowed energy: a localized wavefunction cannot simultaneously have zero kinetic energy. For a free particle on the whole line, the spectral bottom is zero but is unattained by any normalizable wavefunction; see ground-state energy. A lower bound therefore need not describe a physically preparable energy eigenstate.

The ground state supplies a reference for excitation costs and for the quantum variational principle. A ground state is also a stationary state under a time-independent Hamiltonian operator: its quantum phase changes, while its position probability density stays fixed. A nonzero ground-state energy does not imply motion along a classical trajectory, and ground-state degeneracy means there need not be a unique lowest quantum state.