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The Pauli exclusion principle says that each complete one-particle state can have fermionic occupation number zero or one. “Complete” includes spin and any other internal labels, as well as the spatial wavefunction. Thus two electrons can share a spatial orbital with opposite spin projections: these are two different spin orbitals. Equal energy alone does not mean equal quantum state, because degenerate energy levels contain several independent one-particle states.

This distinction explains how an electron shell can accommodate several electrons while exclusion still allows only one per complete one-particle state. It also makes a finite model of fermionic state counting surprisingly simple: two spatial orbitals with two spin choices each give four complete one-particle states, and exactly six two-electron basis states. The following diagram enumerates them; its boxes represent occupation numbers, not locations in space.

Pauli's Exclusion principle and quantum mechanics by Wolfgang Pauli is his retrospective account, delivered on 13 December 1946 for the 1945 Nobel Prize. On printed pp. 29–30, he describes proposing an extra two-valued electron property in autumn 1924 and formulating exclusion in 1925. The crucial clue linked counts of resolved energy eigenstates in alkali spectra under a magnetic field with the populations of closed electron shells. Resolving every label turned a complicated shell capacity into one electron per complete one-particle state. This historical route preceded the modern spin interpretation and the antisymmetric wavefunction formulation; it was not originally a deduction from a Slater determinant.

A superposition of two distinct energy eigenstates gives the expectation value of a time-independent observable an interference term proportional to $e^{-i(E_2-E_1)t/\hslash }$. The displayed beat period applies when that term has nonzero amplitude. A vanishing off-diagonal matrix element, zero state coefficient or equal energies instead gives a constant expectation value.

For a well $-a<x<a$, choose normalized energy eigenstates ${\varphi }_n=a^{-1/2}\sin [(n+1)\pi (x+a)/(2a)]$, $n=0,1,\dots$. The diagonal position matrix elements vanish by the parity operator. For $k\ne n$,To derive it, set $y=x+a$ and use $2\sin Ay\sin By=\cos [(A-B)y]-\cos [(A+B)y]$. For unequal positive integer indices $r,s$, the constant part of $x=y-a$ integrates to zero by orthogonality, whileTaking the difference for $j=r-s$ and $j=r+s$ yields the formula after setting $r=k+1,s=n+1$. It vanishes for equal parity and gives $x_{01}=-32a/(9{\pi }^2)$ for this phase convention.

After the quantum quench, hold $H_f$ fixed and evolve without an intervening energy measurement. The unitary time evolution isProjection onto the original $|0⟩$ gives probability amplitude $c^2{e}^{+i{\Delta }_{f}t/(2\hslash )}+s^2{e}^{-i{\Delta }_{f}t/(2\hslash )}$. Squaring its modulus yields the two-level quantum return probabilityTheir sum is one. For $\theta =\pi /3$, the first minimum of $P_0$ is $1/4$ at $t=\pi \hslash /{\Delta }_f$, and the return is complete at $T=2\pi \hslash /{\Delta }_f$. At $\theta =0$ or $\pi$ there is no oscillation, because the initial quantum state is already a final energy eigenstate.

Changing measurement basis reveals the evolving relative quantum phase. Measuring the final energy first instead destroys this quantum coherence between final energy eigenstates in the unconditioned ensemble: its later original-basis return probability is $c^4+s^4=1-\frac{1}{2}{\sin }^2\theta$, equal to $5/8$ for this example. That constant differs from the oscillation of the unmeasured pure state. The work protocol and the oscillation protocol therefore use separate preparations.

For a nonnegative integer $\ell$, this Coulomb potential energy eigenstate has principal quantum number $\ell +1$ and maximal magnetic quantum number. Put $b=(\ell +1)a$. Including the spherical volume element, its radial probability density is a gamma distribution proportional to $r^{2\ell +2}{e}^{-2r/b}$; its polar density is proportional to ${\sin }^{2\ell +1}\theta$, while its azimuth is uniform. Radial and polar variables are independent. Their moments satisfyThe radial identities follow by successive integration by parts; the angular identity follows from ${\int }_0^{\pi }{\sin }^{j+2}\theta d\theta =(j+1){\int }_0^{\pi }{\sin }^j\theta d\theta /(j+2)$.

Set $h=(2\ell +3{)}^{-1/3}$. Chebyshev's inequality and Markov's inequality give $\mathbb{P}(|r/\mu -1|>h)\le h$ and $\mathbb{P}(|\cos \theta |>h)\le h$. By the union bound, outside an event of probability at most $2h$, the point lies at distance $O(\mu h)$ from the equatorial circle of radius $\mu$. The quantum state therefore concentrates near a classical circular orbit in relative units as $\ell$ grows. The absolute orbit radius and absolute transverse width both grow; this statement does not assert localization in a fixed narrow tube.

Multiplying the quantum harmonic oscillator ground state by $x^2$ produces a quantum superposition of only its $n=0$ and $n=2$ energy eigenstates. In the conventional phase choice for the creation and annihilation operators, $X=\sqrt{\hslash /(2m\omega )}(b+b^{†})$ and $b|0⟩=0$. ThereforeAfter wavefunction normalization, the energy measurement probabilities are $1/3$ at $\hslash \omega /2$ and $2/3$ at $5\hslash \omega /2$. Rephasing the second basis state can change the displayed relative coefficient's sign but cannot change these probabilities. For example, defining the unscaled creation operator as $a_{+}=P+im\omega X=i\sqrt{2m\hslash \omega }{b}^{†}$ reverses the sign of the $n=2$ basis function generated from $(a_{+}{)}^2|0⟩$.

For a positive self-adjoint Hamiltonian operator, finite energy means that a normalized state lies in $D(H^{1/2})$, its form domain, and has expectation value $q_H(\psi )$. This domain can be larger than $D(H)$. With a complete orthonormal basis of energy eigenstates, $\psi ={\sum }_n{c}_n{e}_n$ and $H{e}_n=E_n{e}_n$ give $q_H(\psi )={\sum }_n{E}_n|c_n{|}^2$ by applying $H^{1/2}$ and taking its squared norm. Membership in $D(H)$ instead requires ${\sum }_n{E}_n^2|c_n{|}^2<\infty$. For a Dirichlet free-particle Hamiltonian operator on an interval, the energy form is ${\hslash }^2\int |{\psi }^{\prime }{|}^2/(2m)$ on functions with square-integrable weak derivative and zero endpoint values.

The quadratic Stark effect is an energy level shift whose leading term is quadratic in an applied electric field. For a nondegenerate energy eigenstate of definite parity, the diagonal matrix element of an odd electric-dipole perturbation vanishes. Second-order nondegenerate perturbation theory givesEvery term is negative for the ground state. If field reversal is implemented by the parity operator, an analytic nondegenerate energy branch is even in the field. This symmetry explains the absence of odd powers; it does not apply without qualification to a degeneracy split linearly by the field.

Quantum mechanics describes a quantum system using a quantum state, with observables represented by self-adjoint operators. For a single particle in one dimension, a pure state can be described by a wavefunction $\psi (x,t)$: its squared modulus gives the probability density for position. The Schrödinger equation predicts how this probability amplitude evolves between interventions; measurement in quantum mechanics connects it to experimental outcomes through the Born rule. A wavefunction therefore predicts a distribution of possible positions rather than a single trajectory as in classical mechanics.

The infinite square well makes three central ideas visible with elementary sine functions. Confinement selects discrete energy eigenvalues; wavefunction normalization converts a shape into quantitative probabilities; and a quantum superposition can have a changing probability density even when each constituent energy eigenstate has a stationary one. This combination explains why quantum mechanics uses both linear algebra and differential equations: eigenfunctions describe the building blocks, while quantum phases determine how they interfere. The same tools help explain the discrete energies of chemical atoms and molecules, although their Quantum Hamiltonians require different potentials and often many particles.

In his first 1926 paper, Erwin Schrödinger formulated quantization as an eigenvalue problem for a hydrogen atom in nonrelativistic quantum mechanics. On its opening page he compared the emergence of integers with the number of nodes of a standing wave on a vibrating string. The infinite square well below realizes that appealing idea especially transparently: the allowed integers follow from the boundary conditions. This historical analogy concerns the origin of discrete energies; the Born rule supplies the statistical interpretation of the modern wavefunction. ^[ref].

The position-space kernel of the time-evolution operator propagates a wave function by $\psi (x,t)=\int K_U(x,t;x^{\prime },t^{\prime })\psi (x^{\prime },t^{\prime })d{x}^{\prime }$. It tends to $\delta (x-x^{\prime })$ as $t\to t^{\prime }$. A retarded convention multiplies it by the Heaviside step function: $K_R=\Theta (t-t^{\prime })K_U$. This convention obeys $(i\hslash {\partial }_t-H)K_R=i\hslash \delta (t-t^{\prime })\delta (x-x^{\prime })$; dividing by $i\hslash$ gives the Green function with a unit delta source. The time phase for an energy eigenstate is always $e^{-iE(t-t^{\prime })/\hslash }$.

A quantum quench changes a quantum system's control parameters rapidly and studies the subsequent unitary time evolution. In the ideal sudden limit, write an initial energy eigenstate $|m_i⟩$ using a complete final orthonormal eigenbasis:The Born rule probabilities for a nondegenerate final energy measurement are $|c_n{|}^2$, with ${\sum }_n|c_n{|}^2=1$. For a degenerate energy eigenvalue, sum the probabilities over its orthonormal energy eigenstates. Subsequent relative quantum phases can alter other measurement probabilities even though these final energy populations stay fixed. A quench need not begin in an energy eigenstate; the same expansion applies to any initial pure state.

For a fixed Hilbert space, a bounded self-adjoint Hamiltonian operator with a finite step $H_i\to H_f$ at $t=0$ does not deliver an instantaneous rotation of the quantum state. Integrating the Schrödinger equation across a short interval givesFor a normalized quantum state and $\Vert H(t)\Vert \le M$ in operator norm, the difference has norm at most $2ϵM/\hslash$, which tends to zero. The time derivative can jump even though the quantum state is continuous. Here $\hslash$ is the reduced Planck constant. An instantaneous replacement of the eigenbasis changes coordinates, not the vector being represented.

For a real switch occupying $0\le t\le \tau$, remove any real scalar contribution $a(t)I$ that produces only a global phase, and write $|\tilde{\psi }(t)⟩=e^{i{\int }_0^{t}a(s)ds/\hslash }|\psi (t)⟩$. The same integral argument gives the sufficient bounded-model estimateThus $\epsilon \ll 1$ controls the sudden approximation up to a global phase. For any normalized final energy eigenstate, its probability amplitude differs from the instantaneous-switch value by at most $\epsilon$, and its Born rule probability differs by at most $2\epsilon$. These are sufficient error bounds, not necessary criteria. For the fixed-gap two-level sudden quench, any switching path $H(t)=-\Delta \mathbf{n}(t)\cdot \mathbf{\sigma }/2$ with a unit vector $\mathbf{n}(t)$ has operator norm $\Delta /2$, giving $\epsilon \le \Delta \tau /(2\hslash )$.

This estimate is deliberately for bounded Hamiltonian operators. An unbounded energy spectrum does not supply a finite global $M$; relevant quantum states, operator domains and excited energy eigenvalues require separate control. The adiabatic theorem also requires hypotheses about the path and its spectral gaps; there is no universal switch-duration criterion covering all spectra. The cold-atom collapse and revival after a lattice quench illustrates how a single switch can be sudden for one degree of freedom and slow for another.

The quantum variational principle estimates the lowest energy by choosing a trial wavefunction and computing its expectation value, without solving the Schrödinger equation exactly. Minimizing over a manageable family of trial wavefunctions gives an upper bound; enlarging that family can improve the estimate.

Let $H$ be a self-adjoint operator bounded below, and put $E_{\ast }=\inf \sigma (H)$. For $\Vert \psi \Vert =1$ in its operator domain $D(H)$,Trial states may also lie in the form domain $Q(H)=D((H-bI{)}^{1/2})$, where $b\le E_{\ast }$. Then use the quadratic form of a positive quantum Hamiltonian shifted by $b$:This extends the expectation value beyond $D(H)$ without requiring $H\psi$ to exist. Equality for a normalized state holds exactly in the energy eigenspace at $E_{\ast }$, if that eigenvalue exists. ^[ref].

A short proof makes the direction of the bound memorable. If $H$ has a complete orthonormal basis of energy eigenstates ${\varphi }_n$, writeThe expectation value is a weighted average of allowed energies:Equality requires every occupied energy eigenstate to have energy $E_{\ast }$. ^[ref]. With continuous spectrum, the spectral theorem replaces the sum by an integral against the scalar spectral measure; the same nonnegative-difference argument works.

For an unnormalized trial wavefunction, divide by its squared norm: $R_H[\psi ]=q_H[\psi ]/\Vert \psi {\Vert }^2$ is the form version of the Rayleigh quotient. The quantum variational principle supplies an upper bound on $E_{\ast }$; it supplies neither a lower bound on $E_{\ast }$ nor, by itself, a guarantee that a bound state exists.

To see the method at work, choose the real Gaussian wave packetThe Gaussian integral gives wavefunction normalization and the two useful position averages:Thus its position probability density is a normal distribution with standard deviation $1/\sqrt{2a}$: large $a$ means narrow confinement. In units $\hslash =m=1$, integration by parts and ${\psi }_a^{\prime }=-ax{\psi }_a$ give the kinetic energyThese smooth, rapidly decaying trial wavefunctions belong to the operator domains of both polynomial Quantum Hamiltonians below. Narrowing the Gaussian wave packet increases its kinetic energy; widening it increases the potential energy in either confining potential.

For the quantum harmonic oscillator, take $\hslash =m=\omega =1$:The trial values at $a=1/2,1,2$ are respectively $0.625,0.5,0.625$. The derivative $E_{\mathrm{ho}}^{\prime }(a)=(1-a^{-2})/4$ changes sign at $a=1$, where kinetic energy and potential energy are both $1/4$. Here the trial family contains an exact ground state:The zero-point energy remains positive even at the best width. For comparison, removing the potential leaves $E(a)=a/4\to 0$ as $a\to 0$: the free Quantum Hamiltonian on the line has spectral bottom zero but no normalizable zero-energy energy eigenstate. A sequence of ever broader trial wavefunctions need not approach an actual bound state.

For a pure quartic oscillator, keep $\hslash =m=1$ and set the quartic coefficient to one:The trial values at $a=1,2,3$ are respectively $1,0.6875,0.833333\dots$. Setting the derivative to zero givesThe sign of this derivative changes from negative to positive at the optimum, giving the smallest energy within this Gaussian wave packet family:At this width, $⟨T⟩\approx 0.454280$ and $⟨V⟩\approx 0.227140$, so $2⟨T⟩=4⟨V⟩$, as expected from the power-law quantum virial theorem for a scale-optimized trial wavefunction. The number $0.681420$ is an upper estimate of the ground-state energy, not an asserted exact energy eigenvalue. Indeed,depends on $x$ for every $a>0$, so no member of this trial family is an energy eigenstate. Nevertheless, a single width parameter already turns a difficult Schrödinger equation into a useful, explicit energy estimate.

Choose the Pauli matrices with ${\sigma }_z=\mathrm{diag}(1,-1)$, and let $\omega >0$ be an angular frequency. The computational basis is an orthonormal basis of energy eigenstates for the qubit Hamiltonian operatorIn this convention $|1⟩$ is the lower energy eigenstate; the labels describe a basis choice, not a universal ground state/excited state ordering. Start in the Hadamard basis pure state $|+⟩=(|0⟩+|1⟩)/\sqrt{2}$. ThenThe first factor in the second expression is a global phase. The ratio of the two probability amplitudes has relative quantum phase $\omega t$, so its sign follows directly from $E_1-E_0=-\hslash \omega$.

Multiplying this density matrix by each Pauli matrix and taking its trace gives the Bloch vector:The Bloch vector travels counterclockwise around the equator of the Bloch sphere, from $+x$ toward $+y$ when viewed from $+z$. A computational-basis measurement always has $P_Z(0)=P_Z(1)=1/2$, while the Hadamard basis and ${\sigma }_y$ eigenbasis measurements giveAt $\omega t=\pi /2$, the quantum state is $|+i⟩=(|0⟩+i|1⟩)/\sqrt{2}$ up to a global phase, giving $P_Y(+)=1$. At $\omega t=\pi$, it is $|-⟩$ up to a global phase, giving $P_X(+)=0$. Both retain equal energy measurement probabilities.

At $t=2\pi /\omega$, the time-evolution operator is $U(t)=-I$, so $|\psi (t)⟩=-|+⟩$. The physical quantum state ray, its density operator, and every measurement's probabilities have returned. The representative vector returns exactly only at $t=4\pi /\omega$, when $U(t)=I$. The minus sign is a global phase for this isolated evolution; comparing an evolved branch with an unevolved branch through a controlled unitary gate can make it a relative quantum phase, as explained in global phase of an uncontrolled quantum gate is unobservable.

A Rabi oscillation is a coherent oscillation of populations in a driven two-level quantum system.

A resonant drive can transfer a quantum state from one energy eigenstate to another and then bring its population back. This is unitary time evolution: the drive exchanges energy with the selected two-level system, while total probability stays one. One complete Rabi cycle has population period $2\pi /\Omega$; halfway through, a Rabi pi pulse transfers the whole population in the ideal model. This makes Rabi oscillations useful for calibrating resonant quantum control, preparing quantum superpositions and supplying the pulses of Ramsey interferometry.

The simplest off-resonant explanation is a vibrating polarizability. Let $Q(t)=Q_0\cos (2\pi {\nu }_{v}t)$ be a small normal mode coordinate of molecular vibration, and use one scalar component of polarizability, $\alpha (Q)\simeq {\alpha }_0+{\alpha }_0^{\prime }Q$. For incident electric field $E(t)=E_0\cos (2\pi {\nu }_{0}t)$, the induced electric dipole moment isThe product-to-sum formula produces the two displaced frequencies. A nonzero derivative ${\alpha }_0^{\prime }$ gives vibrational Raman scattering in this linear model. Real polarizability is generally a tensor, and the selected components depend on incident and observed wave polarization. This condition differs from vibrational infrared activity, which requires a changing molecular electric dipole moment without an applied optical electric field. A vibration can therefore appear in one measurement and be absent in the other.

This classical modulation argument explains line locations but supplies equal sideband wave amplitudes; it does not explain their thermal asymmetry or the nonzero Stokes Raman scattering from a vibrational ground state. Those require the quantum harmonic oscillator population and transition strengths. The far-off-resonance drawing uses dashed virtual intermediate levels: they represent terms in a scattering probability amplitude, not a long-lived occupied electronic energy eigenstate. Near an electronic resonance, a more detailed treatment of the intermediate response is needed.

The Schrödinger equation governs the evolution of a quantum state between instances of measurement in quantum mechanics. For a particle of mass $m>0$ moving in a prescribed real potential energy $V(\mathbf{r},t)$, its position wavefunction satisfiesHere $h$ is the Planck constant, ${\nabla }^2$ is the Laplace operator, and the Hamiltonian operator combines kinetic energy with potential energy. Specify an initial wavefunction, an operator domain and any boundary conditions: the differential expression alone does not completely specify a physical model. The Born rule then turns the evolving probability amplitude into position probabilities through $\rho =|\psi {|}^2$ and integration over a region.

This scalar Schrödinger operator describes nonrelativistic quantum mechanics, with relevant momenta much smaller than $mc$, where $c$ is the speed of light. It omits the constant rest energy $m{c}^2$, assumes fixed particle number, and suppresses active spin dynamics and coupling to a magnetic vector potential. A free electron with a fixed, uncoupled spin state can still use this scalar model; the Pauli equation supplies the additional spin components and magnetic coupling when needed. A prescribed real $V$ describes a closed evolution model or an approximation in which the source of that potential energy is treated as external. Dissipation, particle creation and a general measurement in quantum mechanics need further modelling.

For a time-independent self-adjoint Hamiltonian operator, the spectral theorem defines unitary time evolution byInitial states in the operator domain satisfy the differential equation in the Hilbert space sense; the unitary operator also evolves all other states in that Hilbert space. Time-dependent Hamiltonian operators need suitable regularity and domain hypotheses; their evolution is not generally the exponential of $-itH(t)/\hslash$.

The local reason for conservation is especially tangible. Multiply the Schrödinger equation by the complex conjugate ${\psi }^{\ast }$, subtract its conjugate multiplied by $\psi$, and use the fact that the real potential energy terms cancel. For smooth wavefunctions this gives the probability continuity equationThe divergence theorem identifies the change in probability inside a region with minus the outward probability current. Decay at infinity, or appropriate probability-conserving boundary conditions, preserves wavefunction normalization. Conservation of total probability does not require a stationary probability density.

Its usefulness comes from being a linear partial differential equation: quantum superpositions of solutions are solutions, while different quantum phases can produce interference. For a fixed Hamiltonian operator, the time-independent Schrödinger equation finds the energy eigenstates; each then acquires just its own time-dependent quantum phase. One eigenvalue problem therefore organizes both allowed energies and the evolution of arbitrary quantum superpositions, with a continuous spectrum included when required. This is the attractive bridge between a spatial wave problem and a clock: energy differences determine the rate at which relative quantum phases change. It makes atomic spectral lines, quantum tunnelling and quantum scattering calculable from a specified model.

For an explicit example without confinement, take a free particle on the whole line, $V=0$, initially in a Gaussian wave packet with position standard deviation ${\sigma }_0$ and mean momentum $\hslash k_0$:Unlike a single plane wave, this wavefunction satisfies wavefunction normalization. A Fourier transform writes it as a quantum superposition of plane waves. Their dispersion relation is $\omega (k)=\hslash k^2/(2m)$, so each Fourier component gains the factor $e^{-i\hslash k^{2}t/(2m)}$. Completing the square in the resulting Gaussian integral giveswith the square root chosen continuously from $t=0$. Its position probability density and standard deviation areThe centre moves with the group velocity ${\omega }^{\prime }(k_0)=v_0$ and the wave packet spreads because different wavenumbers have different group velocities. This is unitary wave dispersion, without a random force or loss of probability. Independently, the initial momentum standard deviation is $\Delta p=\hslash /(2{\sigma }_0)$ and the initial position-momentum covariance vanishes. Free evolution gives $x(t)=x(0)+p(0)t/m$ in the Heisenberg picture, henceThis independently checks the spreading law. The Gaussian integral of $\rho$ is one at every time; the decreasing peak is exactly offset by increasing width.

As hypothetical preparation parameters, choose a free electron with ${\sigma }_0=1\mathrm{nm}$ and $k_0=2{\mathrm{nm}}^{-1}$. Using $\hslash \simeq 1.054571817\times 10^{-34}\mathrm{J}\mathrm{s}$ and $m\simeq 9.1093837\times 10^{-31}\mathrm{kg}$ givesThe rounded electron mass uses the 2022 adjustment.^[ref] At $t=t_s$, the centre is $4\mathrm{nm}$ and ${\sigma }_t=\sqrt{2}\mathrm{nm}$; at $t=2t_s$, they are $8\mathrm{nm}$ and $\sqrt{5}\mathrm{nm}$. The mean kinetic energy staysIt includes both mean motion and the momentum spread. The mean speed is about $7.72\times 10^{-4}c$ and the momentum spread corresponds to $1.93\times 10^{-4}c$, making the nonrelativistic model accurate for the appreciably occupied part of this ideal Gaussian distribution. Its mathematically unbounded tails are an idealization.

The complex width also explains where the probability goes. Write $\psi =\sqrt{\rho }{e}^{i\theta }$, where $\theta$ is the dimensionless quantum phase. Differentiating the exact solution givesRelative to the moving centre, the probability current $j_{\mathrm{rel}}=j-v_0\rho$ points outward on both sides for $t>0$. This is a flux statement, not an additional assumption about individual particle trajectories. At $t=t_s$ and $x-v_{0}t=\pm {\sigma }_0$, the relative flow speeds $j_{\mathrm{rel}}/\rho$ are $\pm {\sigma }_0/(2t_s)$, about $\pm 2.8942\times 10^4\mathrm{m}{\mathrm{s}}^{-1}$. The probability within a moving interval of half-width ${\sigma }_0$ falls from about $0.6827$ initially to $0.5205$ at $t_s$, exactly because of this outward probability current.

Historically, the 1926 Quantisierung als Eigenwertproblem (Erste Mitteilung) by Erwin Schrödinger began with the stationary hydrogen atom problem. It distinguishes discrete negative energies from a positive continuous spectrum; it is not yet the general evolution equation displayed above.^[ref] The opening of quantum mechanics discusses its original vibrating-string analogy.

In the 12 December 1933 lecture The fundamental idea of wave mechanics by Erwin Schrödinger, Erwin Schrödinger explains the move from independent rays to waves through diffraction, then applies that analogy to atomic physics. His closing pages explicitly acknowledge the difficulty of reconciling wave language with observed particle tracks. This retrospective physical argument motivates the model; it does not derive the modern Born rule from classical mechanics.^[ref]

The dates separate proposal from measurement: the de Broglie wavelength belongs to the 1924 thesis, the Schrödinger equation to 1926, and the Davisson–Germer experiment's electron diffraction beams to 1927.^[ref] That linked experiment describes the prepared nickel crystal, evacuated electron gun, angular collector scans, retarding-potential selection and heating controls. Its measured collector electric current tests wave-dependent scattering probabilities; it neither measures a wavefunction directly nor establishes this equation uniquely.

Insert a complete resolution of identity in energy eigenstates on either side of the time-evolution operator. Each state evolves by its scalar energy phase, yielding the displayed quantum propagator. Its spectral sum includes an integral over any continuous spectrum, with the measure fixed by the continuum normalization. Omitting the scattering states when bound states are also present destroys completeness and the delta-function short-time limit.

In 1913 Johannes Stark reported that an applied electric field resolved the hydrogen $H_{\beta }$ and $H_{\gamma }$ spectral lines into five components at his instrument's spectral resolving power, viewed perpendicular to the electric field. Three inner components had polarization of an electromagnetic wave perpendicular to the electric field; two outer components had it parallel.^[ref]

In his lecture of 3 June 1920 for the 1919 prize, Johannes Stark describes canal rays emerging through a perforated cathode into the electric field between it and a supplementary electrode. A spectrograph recorded the emitted light. His earlier Doppler effect comparison used a collimator perpendicular to the beam and then along approaching rays. Later beam/electric field reversal changed component intensities.^[ref]

The historical account distinguishes observation perpendicular to the electric field, with five resolved components, from observation parallel to it, with three. These are viewing directions, distinct from the direction of the polarization of an electromagnetic wave.^[ref]

The experimental distinctions matter. Changing the viewing direction tests a Doppler effect contribution; changing the applied electric field tests the Stark effect; analyzing polarization of an electromagnetic wave separates components that may overlap in an unpolarized record. A comparison with the unperturbed spectral line fixes the origin of a displacement. These are different controls, and the earlier Doppler effect comparison should not be described as a field-off control of the later discovery. A spectrograph's finite spectral resolving power can merge several components into one. In particular, a count of visible spectral lines does not by itself count all energy eigenstates.

For a modern idealization of the gap, an electric potential difference $\Delta V$ over separation $d$ gives $|\mathcal{E}|\simeq |\Delta V|/d$ only if edge effects and the charge density in the gas are negligible. This is a calibration model, not a historical value assigned to Stark's apparatus. Similarly, a canal ray beam need not be a pure beam of neutral excited hydrogen atoms; the quantum mechanics model below isolates one neutral hydrogen atom from the source's preparation and collision processes.

An electric field shifts and can split the energy eigenvalues of an atom. This is the Stark effect; its hydrogen atom ground-state case is quadratic in a weak field.

The observable in Stark effect spectroscopy is a change in a spectral line, rather than a direct reading of an individual energy eigenvalue. If an upper energy eigenstate $u$ emits a photon into a lower energy eigenstate $l$, the Planck constant $h$ relates its frequency to the difference:Here $\mathcal{E}$ denotes the applied electric field component along a chosen axis. Both levels can move, and electric-dipole selection rules for hydrogen decide which pairs produce observable spectral lines. This makes Stark effect spectroscopy a probe of energy eigenstates and their electric dipole moments: the slope $-\partial E/\partial \mathcal{E}$ is the corresponding dipole component by the Hellmann–Feynman theorem. The comparison with Zeeman splitting is useful: there an applied magnetic field supplies the perturbation.