The stationary Schrödinger equation is
The Laplacian represents the kinetic-energy operator. For a spherically symmetric function, . The attractive Coulomb potential of the nucleus is ; is the energy eigenvalue. Multiplication by produces the displayed radial equation with Bohr radius
For a normalizable bound state, write and take . Substitution of in
gives, after division by the exponential, the coefficients
If and , these force and . If , the first coefficient gives , the second gives , and the third gives . Up to nonzero scalar factors, the two radial bound states and their energies are consequently
They are linearly independent as functions and correspond to different energy eigenvalues. Strictly, they are not two solutions of one fixed-energy differential equation: each is a solution at its own energy.
For the higher-energy state, the spherical Born rule includes the radial factor . Its normalization constant and the angular factor cancel in the ratio
The given integral formula makes the denominator and the numerator . Thus
The Born rule assigns to a projective measurement with projection operators . Its numerical form can be shared by theories while the source of the probabilities differs. Comparing Bohmian mechanics, the GRW model and the many-worlds interpretation exposes three different roles: uncertainty over actual configurations, fundamental stochastic events, and weights for branch-relative expectation.
In Bohmian mechanics, the Schrödinger equation implies a probability continuity equation for with current , while the guidance equation transports an ensemble density with velocity :
Thus is preserved: quantum equilibrium equivariance. If an apparatus interaction produces disjoint configuration regions with occupied-branch norm , integrating the equilibrium distribution gives . The actual outcome is fixed by initial configuration; the distribution describes the typical or uncertain configuration, not a fundamental random collapse. Equivariance alone does not prove equilibrium initially: every admissible density is transported by the velocity field. A typicality account privileges the equivariant measure and then explains subsystem statistics conditionally; that explanatory premise must not be hidden in the continuity equation.[ref]
In the GRW model, the centre law is part of the stochastic dynamics. Since , it is normalized. For two well-separated correlated pointer packets with coefficients , integration over centres around their respective occupied regions gives approximately ; cross-contributions are suppressed at separations large compared with . This explains why macroscopic records follow the Born rule approximately, without a special postulate applying only when an observer measures. However, the squared-norm centre law already carries the relevant mathematical probability structure. The theory relocates the rule into a universal physical law; it does not derive all probabilities from a deterministic equation. There are also small predicted deviations from standard unitary quantum mechanics.[ref]
In the many-worlds interpretation, every nonzero decohering component persists, so the question is not which single global branch will survive. It is why a rational observer should use branch weight for expectation or caring about successor records. Equal-amplitude symmetry and decision theory motivate equal weights for physically equivalent alternatives. For rational , an ancillary refinement into equal-norm alternatives can motivate weight , followed by continuity for other amplitudes. This argument requires assumptions that refining irrelevant details does not change value, that preferences respect the relevant quantum symmetries, and that weight tracks the intended notion of expectation. Those are substantive premises, not consequences of branch existence alone.[ref]
Naive branch counting is unsuitable: decoherence yields approximate, refinement-dependent branches, and splitting one record into more environmental records should not change its weight. Nor is diagonality of a density matrix already an account of probability. The comparison therefore has no common derivation from bare formalism. Bohmian mechanics needs a justified equilibrium or typicality measure, GRW model needs a justified stochastic law, and an Everettian account needs a justified connection from branch structure and rationality to experienced statistics. Each offers a coherent location for the Born rule; the remaining explanatory costs differ.
The Pusey-Barrett-Rudolph theorem excludes overlapping preparation distributions for distinct pure states in an ontological model of a quantum system satisfying preparation independence and the specified quantum predictions. It excludes neither all hidden variables nor every informational use of a quantum state. The precise overlap criterion is essential: a psi-epistemic model lets at least two distinct pure-state preparations assign positive common probability mass to the same underlying states; a psi-ontic model has mutually singular measures for each distinct pair.[ref]
Let preparation sample from . A fixed quantum measurement has nonnegative response functions with . Averaging over the preparation must reproduce the Born rule. The response is fixed by and the complete underlying state, not by additional knowledge of the preparation label. No outcome determinism or Bell local causality is assumed; the joint measurement response need not factor into local responses. For independently operated preparations, preparation independence further identifies the joint state space with the appropriate product and assigns
Operationally independent devices do not logically entail this ontic factorization; it is an additional physical premise.[ref]
The two-qubit example can be checked directly. Set . In computational basis order , take the following normalized columns as an orthonormal basis:
Their pairwise inner products vanish. Direct multiplication shows that the respective preparations have zero probability amplitude for respective outcomes . This is the PBR exclusion measurement for zero and plus: the measurement does not perfectly distinguish the preparations, but each outcome rules one out.
Suppose a common submeasure of and has mass ; with densities one can take . Preparation independence makes a common submeasure of all four product preparations, of mass . The zero probability for outcome under its excluded preparation and nonnegativity force
Summing and using normalization yields , a contradiction. This measure formulation avoids treating a set with merely nonempty topological support as a positive-probability overlap.
For arbitrary distinct nonorthogonal pure states, write , with overlap and . The general proof constructs an exclusion measurement on independently prepared copies when . A finite always exists. The same common-submeasure contradiction then excludes positive overlap. Orthogonal preparations are already disjoint if their perfectly distinguishing measurement is reproduced. The original paper also bounds residual overlap for imperfect exclusion data; exact disjointness concerns the ideal theorem, not a finite experiment's proof of exact zero.[ref]
The scope is consequently sharp. Bohmian mechanics is not excluded: its underlying state includes the wave function, making distinct pure preparations disjoint even though extra configuration variables remain. A psi-ontic model need not be complete with the wave function alone, and the theorem does not identify the wave function with a three-dimensional material field. Models abandoning preparation independence, or accounts not representing preparations as uncertainty over observer-independent states of this specified kind, are outside this conclusion. Epistemic uncertainty between mixed preparations is not banned. Nor does the theorem establish a collapse mechanism, choose between Bohmian and Everettian theories, or solve the measurement problem. Its achievement is a conditional impossibility theorem about a precise form of pure-state epistemic overlap.
Quantum decoherence explains the practical stability of records and suppression of observable interference; it does not alone select one outcome. The measurement problem arises when universal unitary time evolution, a complete wave function description and a unique definite outcome are all demanded. A theory must explain which commitment is changed or supplemented, not merely replace a pure composite description by a reduced one.
Model an ideal quantum measurement and its environment by
Taking the partial trace over the environment gives the system–apparatus reduced density matrix
Environmental records make very small for macroscopically distinct alternatives. If independent fragments have overlaps , their combined overlap is , explaining the rapid suppression. The apparatus interaction also favours robust records, giving environment-induced pointer-basis selection rather than an arbitrary choice of basis.[ref]
What follows is approximate agreement, for local apparatus observables, with a classical probabilistic mixture. What does not follow is that either term has ceased to exist. Even with orthogonal environmental records, the global quantum state is a pure state with quantum entanglement. For orthogonal branches , the global observable has expectation in the superposition and zero in the corresponding incoherent mixture. Its practical inaccessibility is not its mathematical disappearance. The reduced state is an improper mixed state, not proof that an unknown single branch was selected.
Different interpretations use this result differently. In Bohmian mechanics, disjoint environmental configurations make one occupied branch an effective description of the actual apparatus. In the many-worlds interpretation, robust branches supply approximately autonomous relative records, without a unique global outcome. In the GRW model, a separate stochastic change of the wave function selects a dominant component; environmental decoherence helps explain ordinary records but is not the collapse law. These are different completions of the argument.
Nor does diagonality derive the Born rule. Interpreting the diagonal entries as experienced outcome probabilities requires a probability rule or an interpretive argument. Extremely small overlaps also leave approximations and possible quantum recoherence; a finite controlled environment can in principle be manipulated to reveal the global coherence. The appropriate verdict is that decoherence resolves much of the preferred-record-basis and effective-classicality problem while leaving the unique-outcome and probability problems dependent on further theory. It is an essential physical mechanism in many accounts, not a self-contained solution by relabelling a partial trace as collapse.
The angular-momentum commutators give
For example . In the displayed basis , the only nonzero upper entries of connect adjacent magnetic quantum numbers. Subtracting their column and row eigenvalues multiplies each by , proving the first matrix commutator; the lower matrix similarly gives the second. Direct multiplication gives
whose difference is . Also , confirming .
A rotation changes the quantization axis without changing the spectrum, so has eigenvalues . Its dimensionless matrix is
Solving and normalizing gives the spin-one maximum-projection eigenvector
For instance the first equation is , and the squared components sum to one. An overall phase is immaterial.
At , . The Born rule therefore predicts, in the requested order,
This treats the Stern-Gerlach experiment as the stipulated ideal measurement of orbital projection. In an actual atom, other magnetic moments and spin-orbit coupling can change which angular momentum the apparatus resolves.
A pure quantum state is a unit ray in a complex Hilbert space: normalization fixes total probability, a common phase is unobservable, and superpositions retain relative phases. Observables are self-adjoint operators. For an ideal projective measurement with spectral projector , the Born rule gives and the Lüders rule gives conditional state . This preserves an eigenspace, not necessarily a unique vector when the outcome is degenerate. Between measurements, a closed system evolves unitarily according to . Composite systems use tensor products; quantum statistics additionally restrict identical-particle states. These are a framework supported by many experiments, not separate logical deductions from any one experiment.
In the photoelectric effect, monochromatic light illuminates a clean metal and a retarding potential measures the largest emitted electron kinetic energy. frequency controls the stopping energy, , while in the one-photon regime intensity mainly controls the emission rate. A threshold frequency and a stopping-energy slope support quantized energy exchange rather than gradual absorption of arbitrary classical-wave energy by each electron. Contact potentials, surface contamination, dark current and spectral impurities require controls. Robert Andrews Millikan tested the frequency–stopping-potential relation with careful surface and electrical control.[ref]
The Stern-Gerlach experiment sends a collimated neutral silver beam through an inhomogeneous magnetic field onto a detector. The force is approximately in an appropriate strong-field electronic description. Two resolved components rather than a continuous classical orientation spread support discrete angular-momentum projections. Field-off beam profiles and magnetic-gradient/beam-width controls distinguish splitting from ordinary broadening. In the modern description the silver ground electronic state has ; the 1922 experiment preceded the electron-spin interpretation. Ideal sequential analyzers along different axes illustrate incompatible observables and state preparation, but were not the original apparatus.[ref]
In the Davisson–Germer experiment, accelerated electrons scatter from a nickel single crystal and an angularly scanned collector measures the scattered intensity. Changing voltage and crystal orientation changes narrow diffraction maxima. The inferred wavelength agrees with , with nonrelativistic . vacuum, crystal cleaning, energy selection and background measurements matter: adsorbed surface gas can produce additional diffraction features. This supports matter-wave amplitudes and interference, with measured intensities related to their squared magnitude; it does not mean an electron must follow a classical orbit through the apparatus.[ref] Together these experiments motivate quantized outcomes, wave amplitudes and probabilistic measurement while leaving a distinction between observed evidence and the general postulates used to organize it.
The Born rule uses the squared modulus, so the imaginary term contributes positively: . For , wavefunction normalization would multiply the supplied expression by . Equivalently, take the ratio of the integrals directly:
Using instead of would fail to produce a real, nonnegative probability density.
Stationary states. Inside the infinite square well, the time-independent Schrödinger equation has sinusoidal solutions. The boundary conditions select ; normalization then gives
Each wavefunction vanishes outside the well. There is no nonzero state.
Immediate energy measurement after expansion. For the one-sided sudden expansion of an infinite square well, take the original wall at as fixed, so the expanded well occupies . In the sudden approximation, the initial wavefunction remains on , extended by zero elsewhere. The new ground state is . Its probability amplitude is
The Born rule therefore gives
The motion of the walls matters: a symmetric expansion about the old midpoint would instead give . The stated width alone does not explicitly identify the final endpoints. The first result uses the natural continuation of the specified left boundary; if both boundaries are moved, the final location must be supplied. For a new well containing , the overlap is .
Evolution of one energy eigenstate. For a time-independent Hamiltonian operator, write . Substitution into the Time-dependent Schrödinger equation gives , so
Only a global phase changes, leaving all measurement probabilities unchanged.
Delayed energy measurement. Expand the unchanged initial state in the complete new energy eigenbasis,
For the fixed-left-wall geometry, direct overlap integration gives
orthogonality isolates the new ground-state amplitude as . Its phase cancels on squaring, so the ground-state probability remains for every delay, provided the expanded well remains fixed and no intervening measurement or environment changes the state. The position probability density generally evolves because different eigenstates acquire different relative phases.
With two coherent paths, the probability amplitude at a screen is . The Born rule gives
The final term shifts when the relative phase changes, producing interference fringes. For slit separation in the far field, the phase difference is approximately ; constructive interference occurs at . Finite slit widths add a diffraction envelope, so an ideal equally bright, infinitely narrow slit model does not predict the full observed envelope.
single-electron interference pattern buildup starts with isolated localized detector events at sufficiently low source intensity. Repeated events accumulate the interference probability distribution. Thus detection is discrete while propagation is described by coherent probability amplitudes. The effect cannot be explained by interference between different particles if the apparatus is occupied by at most one particle at a time. A motivating realization used a field-emission electron source, an electron biprism to recombine two paths, electron lenses and a position-sensitive electron counter; it recorded individual arrivals building up the fringes. This was a biprism realization of two-path interference, not a plate with two literal slits.[ref]
The crucial comparison is between both coherent paths open and a preparation that supplies which-path information. If the paths become correlated with detector states , the joint state is . Ignoring that detector multiplies the interference term by . Orthogonal detector states remove the term completely, while identical detector states preserve it. This is a consequence of entanglement and the partial trace; a human need not read the detector.
In a real test, check the single-path distributions, detector background, source coherence and stability of the relative phase. Classical phase drift can wash out fringes without supplying which-path information. Conversely, localized detections alone do not establish coherent two-path propagation; the controlled phase dependence of their accumulated distribution provides the discriminating evidence.
For a nonrelativistic spinless particle in a scalar potential, the Time-dependent Schrödinger equation is
An initial wavefunction together with boundary conditions specifies the evolution. The Hamiltonian operator must be self-adjoint on the appropriate domain for closed-system evolution to be unitary. The equation is linear, so a superposition of solutions is another solution. Its complex wavefunction predicts probability amplitudes; the Born rule separately supplies the connection to measurement probabilities.
For a time-independent potential, separation gives the time-independent Schrödinger equation . Normalizability and boundary conditions select the allowed energies of bound states; scattering states instead use incoming and outgoing boundary conditions and generalized normalization. A general state is a superposition of energy eigenstates, with a spectral integral as well if there is a continuous spectrum. Different energies accumulate different phases, allowing time-dependent position densities and oscillatory expectation values even though a single energy eigenstate has a stationary density.
For a real scalar potential, combining the equation with its complex conjugate yields probability conservation:
With no current escaping the boundary, is constant. Matching conditions at a finite potential step follow from the differential equation and enforce the flux balance used in B6.
The Schrödinger equation is a dynamical postulate of nonrelativistic quantum mechanics, not a consequence of classical mechanics alone. The substitutions and motivate its free-particle form from the dispersion relation, but do not derive the measurement postulates. The scalar equation omits intrinsic spin and relativistic particle creation. Spinful or relativistic problems require the corresponding extended theory. Nor does its deterministic unitary evolution, by itself, prescribe conditioning on a particular observed measurement outcome.
Operators, quantization and rotations. Angular momentum is the generator of spatial rotations. In quantum mechanics, its components are Hermitian operators on their appropriate domains and obey
These angular momentum commutation relations prevent all three components from having simultaneous sharp values. For example, the Robertson uncertainty principle gives . One conventionally diagonalizes and a selected component :
The allowed labels are and . An angular-momentum multiplet has states. The magnitude differs from the largest possible component ; the remaining components fluctuate even in a state with maximal .
The angular momentum lowering operator and its raising counterpart, , satisfy
The ladder terminates at . A rotation through angle about unit vector acts through the unitary operator . Thus quantized components and the continuous rotation of a state are compatible.
Orbital angular momentum. The orbital contribution is associated with motion in space:
For a spinless spatial wavefunction, the simultaneous angular eigenfunctions are the spherical harmonics , with and . Single-valued ordinary scalar spatial wavefunctions give integer orbital labels. In a central potential energy, , so stationary states may be labelled by these angular quantum numbers. The angular kinetic contribution appears in the radial equation as , the centrifugal potential. Noncentral interactions need not conserve these orbital labels.
Intrinsic spin and addition. Spin angular momentum is an intrinsic internal degree of freedom with the same commutation algebra. It is not the angular momentum of a small classical charged sphere literally rotating about its centre. For an electron, and , so in terms of the Pauli matrices. Its squared spin is . Other particles can have integer or half-integer spin, including spin zero.
For one particle with orbital and spin degrees of freedom, ; the two component sets commute with each other. Addition of angular momentum permits . The coupled states are linear combinations of the uncoupled with , determined by Clebsch-Gordan coefficients. A rotationally invariant spin-orbit interaction can conserve while mixing the separate component labels.
Angular momentum also carries a magnetic moment. For an electron's orbital motion and intrinsic spin,
The minus signs reflect negative electric charge. With the Bohr magneton , a spin projection has . A magnetic field can therefore distinguish angular-momentum states through their interaction energy .
Stern–Gerlach measurement. In the Stern-Gerlach experiment, atoms emerge from a heated source, pass through collimating apertures, traverse a strongly inhomogeneous magnetic field, and strike a position-sensitive screen. The beam is neutral, so its separation is interpreted through the atomic magnetic moment rather than the ordinary charged-particle Lorentz force. Near a chosen quantization direction, the interaction gives
A uniform field can exert a torque but would not separate the beam by this translational force; the gradient is essential. Different allowed magnetic-moment components become correlated with different trajectories. A classical ensemble with continuously varying orientations would yield a continuous spread, whereas discrete quantum components yield separated channels.
In the modern electronic description of ground-state silver, filled shells cancel their electronic angular momenta and the unpaired electron has , , . The effective electronic measurement therefore has two components, approximately , rather than an orbital , which is not allowed. For positive field gradient the electronic component has negative and deflects downward in this coordinate convention. Nuclear spin and hyperfine structure are neglected in this simplified two-channel account. Historically the original splitting preceded the electron-spin interpretation, so the modern explanation should not be confused with the original investigators' interpretation.
Figure 1.
A neutral atomic beam separates into two electronic magnetic-moment channels in a field gradient
. Details.
More generally a prepared spin state gives the two outcomes with probabilities . Selecting one channel prepares a state for further measurements. An ideal second analyser along the same axis then gives a definite result, whereas one along a perpendicular axis gives two equally likely outcomes for a spin-one-half eigenstate. This connects the apparatus directly to incompatible spin components and the Born rule. Angular momentum is quantized through its operator algebra; the Stern–Gerlach gradient turns that discrete internal information into spatially distinguishable outcomes.
A Hermitian operator satisfies the adjoint symmetry condition
for vectors in its specified domain. For a finite matrix this means . For an unbounded differential operator, boundary conditions and domains matter: symmetry on a chosen domain is not alone sufficient for self-adjointness. Physical observables require the corresponding self-adjoint operator and its spectral measure. This distinction prevents purely formal integration by parts from being mistaken for a complete operator definition.
Real eigenvalues. If with nonzero norm, Hermiticity implies
so . Thus eigenvalues representing measurement outcomes are real.
Orthogonality. For eigenvectors ,
Hence , and distinct eigenvalues have orthogonal eigenvectors. Within a degenerate eigenspace, Gram-Schmidt orthogonalization can choose an orthonormal basis. In finite dimensions the spectral theorem gives a complete orthonormal eigenbasis and
where projects onto each eigenspace. In infinite dimensions a continuous spectrum may require a spectral integral rather than a normalizable eigenvector for every possible outcome; a position operator on the full line is a familiar example.
Measurements and probabilities. In the discrete case the Born rule assigns probability to the outcome . For a nondegenerate eigenbasis, gives probabilities , with
The variance vanishes precisely when the state lies in an eigenspace with a single sharp outcome. A repeatable ideal projective measurement prepares the corresponding eigenspace; superpositions of different eigenvalues do not have a preassigned sharp value of that observable in this description.
Compatibility and dynamics. Commuting Hermitian matrices admit simultaneous diagonalization, permitting a common set of sharp labels. For example commute, whereas do not. In the differential-operator setting the corresponding spectral compatibility requires appropriate domain conditions. Noncommuting observables obey the Robertson uncertainty principle
The canonical commutation relation then gives .
The Hamiltonian operator represents energy. A self-adjoint generates unitary time evolution, , preserving norm and total probability; its eigenvalues determine stationary-state phases and transition energies. Hermiticity supplies real outcomes and orthogonal eigenspaces, while self-adjointness and the spectral theorem make these measurement and evolution rules mathematically complete.
Expand the initial wavefunction in the angular momentum eigenbasis using . With the normalized from part (a), this gives
The coefficient squares sum to one, also verifying the stated normalization. The Born rule therefore gives angular momentum outcomes
For an energy measurement the two distinct states belong to the same energy eigenspace. Sum their probabilities, rather than adding their amplitudes, to obtain
Their relative probabilities are for the angular momenta and for the energies. In particular, zero mean angular momentum does not imply zero rotational energy.
The postulates of quantum mechanics give a framework for predicting observations from a prepared state. The experiments below motivate different features of that framework; no one experiment proves the whole set of postulates or specifies every Hamiltonian operator.
A pure quantum state is a normalized vector in a complex Hilbert space, with vectors differing by an overall quantum phase representing the same physical preparation. In position representation, . The linear state space permits quantum superposition, while the Born rule assigns probability to a position outcome in a region . The wavefunction is a probability amplitude; it is not a classical distribution of definite particle positions and momenta.
An observable is represented by a self-adjoint operator. If has spectral projectors , its possible measurement outcomes are its spectral values and . The mean is . For an ideal repeatable projective measurement, obtaining leaves the normalized conditional state . This projects onto an entire eigenspace if the outcome is degenerate. General detectors need more general measurement in quantum mechanics models; the projective update is an idealization. Noncommuting observables need not have simultaneous sharp values, as the canonical commutation relation and Heisenberg uncertainty relation illustrate.
Between measurements, an isolated system has unitary time evolution generated by its Hamiltonian operator:
This preserves normalization and superpositions. Composite systems use a tensor product of state spaces, allowing entangled states as well as product states; identical particles additionally require the bosonic or fermionic exchange symmetry appropriate to their species. Statistical mixtures are described by a density matrix, with . These rules separate preparation, coherent evolution and measurement.
The photoelectric effect exposes discrete energy transfer by light. Illuminate a clean metal cathode in an evacuated tube and measure the collected electron current while varying the light frequency, intensity and a retarding voltage. The stopping potential probes the largest emitted electron kinetic energy, whereas the photocurrent measures the rate at which charge is collected. In the ordinary single-photon regime there is a threshold frequency; above it the maximum energy grows with frequency, rather than with intensity. Changing intensity at fixed frequency mainly changes the number of emitted electrons. These observations are summarized by the Einstein photoelectric equation
Here is the surface work function, and the stopping voltage is understood after any photoelectric contact-potential correction. A photon delivers in an absorption event; emission is allowed only when that energy can pay the escape cost. This accounts for the frequency threshold and the lack of the classical waiting time associated with slowly accumulating energy in a single electron. The experiment supports energy quantization of light; it does not imply that every incident photon emits an electron or that every emitted electron has the maximum energy. Surface losses and collection geometry affect the full current-voltage curve.
The Davisson–Germer experiment demonstrates a complementary wave property of matter. An electron gun uses a heated emitter, accelerating voltage and apertures to send a narrow beam onto a nickel single crystal in vacuum. A movable collector measures scattered electric current versus direction; rotating the crystal also tests its azimuthal symmetry. The crystal gives sharp angular beams whose positions depend on voltage and crystal orientation. A prominent feature occurs near accelerating voltage and roughly detector colatitude. The nonrelativistic de Broglie wavelength predicted at that voltage is
Diffraction wavelengths inferred using the known crystal structure agree with this voltage dependence. These angular peaks arise from coherent addition of scattering amplitudes from the crystal, not from classical specular reflection of independent point projectiles. Bragg's law is for lattice-plane spacing and angle to those planes; a detector colatitude is a different angle and must not be substituted without its geometry. The historical readout was current, not a photograph of individual electron trajectories.[ref]
The double-slit experiment makes the role of amplitudes especially direct. A coherent source illuminates two narrow slits; an observation screen a distance away records the pattern. For slit spacing and small screen displacement , the path difference is approximately . The two amplitudes add before probabilities are formed:
For equal coherent illumination the interference term varies as , giving fringe spacing beneath the single-slit diffraction envelope. Blocking one slit removes that cross term. Young's optical experiment established wave interference; later particle-resolved realizations with photons or electrons show localized detection events whose accumulated distribution has the interference pattern. Low arrival rates demonstrate that this pattern does not require different incident particles to collide with one another.
If the paths become correlated with distinguishable detector states and , the cross term acquires their overlap . Perfectly distinguishable path records make that overlap zero, suppressing interference even if the spatial beams still overlap. This connects quantum entanglement, measurement and loss of observable coherence. Without a path measurement, the two alternatives are amplitudes for one preparation, rather than classical mutually exclusive events whose probabilities may simply be added.
Together these experiments motivate a description in which energy transfer and detector outcomes can be discrete, yet propagation retains complex quantum phases and interference. The Born rule connects those amplitudes to repeatable frequencies of outcomes. The Schrödinger equation supplies the dynamics once a Hamiltonian operator is specified, while observable operators, state preparation and the measurement model specify what the apparatus can read.
Put , including its sign. The initial vector is the eigenstate of ; it is not an energy eigenstate of . In terms of the spin eigenstates found above, . Each energy eigenstate acquires its own unitary time evolution phase:
Equivalently, follows from . The Born rule gives
The expectation value of the spin angular momentum is , a rotation around the axis. Its direction follows the specified sign of the Hamiltonian; changing the magnetic coupling sign reverses the precession.
A localized quantum particle is described by a wave packet: a coherent quantum superposition of momentum components, rather than a single delocalized plane wave. The Born rule assigns the position probability density . A useful normalized initial Gaussian wave packet is
Its mean position and momentum are and , and its standard deviations satisfy , . This unchirped initial state saturates the Heisenberg uncertainty relation.
For a free particle, the momentum-space Schrödinger equation multiplies each amplitude by . The inverse Fourier transform is a Gaussian integral, giving the free Gaussian wave packet evolution
One way to obtain this expression explicitly is to write the initial momentum amplitude as proportional to , multiply by the free evolution phase and complete the square in . Taking the modulus squared removes the position-dependent phase and leaves
The expectation value follows uniform classical motion while the density spreads. A narrower initial packet needs a wider momentum distribution and therefore spreads more rapidly. At long times its width grows linearly with ; its variance grows quadratically, unlike the linear variance growth of ordinary diffusion. The probability continuity equation preserves total probability despite the decreasing peak height. The mean momentum and the mean energy remain constant, since the momentum populations do not change.
The same result has a wave interpretation. For a free nonrelativistic particle , so the group velocity is , equal to at the packet center. The curvature makes different momentum components travel with different group velocities, producing dispersion. The phase velocity is for this energy convention and does not describe the motion of the envelope. The evolving quadratic spatial phase is essential to the spreading; a density snapshot alone does not specify the full quantum state.
A freely spreading Gaussian wave packet remains a pure Gaussian state but develops position-momentum correlations. Its symmetrized covariance is . Consequently
Equality in the Robertson-Schrödinger uncertainty relation survives at every time, whereas the simpler product equals only initially. A chirped Gaussian wave packet can already have . More generally, gives . A sufficiently negative initial covariance permits initial contraction before subsequent spreading.
Figure 1.
Free Gaussian spreading, constant coherent-state width and the breathing width of a squeezed state
. Details.
A potential energy changes this behavior. A quadratic potential preserves the Gaussian form because the evolution of position and momentum is linear. For a quantum harmonic oscillator, the Gaussian covariance in a harmonic potential is
A coherent state has , and zero centered covariance. Its width is constant, and its center follows . In oscillator notation its coherent state label rotates as , apart from the common ground-energy phase of the state vector. A squeezed coherent state generally has a width that breathes at . Thus being Gaussian does not imply either free spreading or constant width; the Hamiltonian operator and initial covariance determine the result.
For a general nonquadratic potential, different parts of the packet experience different nonlinear forces, and an initially Gaussian profile need not remain Gaussian. Ehrenfest theorem gives the exact relations and . Replacing the last mean by is exact for a quadratic potential and approximate for a packet narrow compared with the scale on which the force varies. This connects packet motion to the correspondence principle without treating a quantum state as a definite classical path. Scattering can split a packet into reflected and transmitted components, while confinement can produce oscillations and interference between discrete energy eigenstates. Their relative phases evolve even when their populations remain constant. Localization, spreading and coherent motion all follow from the same linear unitary time evolution.
An observable is represented by a self-adjoint operator. For an ideal projective measurement, let be its spectral projector for outcome . The Born rule gives , or for a density matrix . Conditional on obtaining , the Lüders rule gives
For a degenerate outcome this projects onto the whole associated eigenspace, rather than arbitrarily selecting a vector within it. An immediate repeated ideal measurement returns the same outcome, provided there is no intervening evolution or disturbance.
Commuting finite-dimensional observables admit a common orthonormal eigenbasis; their projectors commute and ideal joint measurements are compatible. Noncommuting observables generally have no complete common eigenbasis, and measurement order can affect the subsequent statistics. Particular common eigenvectors can nevertheless exist, so a nonzero commutator does not mean that every state has a nonzero uncertainty in both quantities.
For a quantitative constraint, apply the Cauchy-Schwarz inequality to and . The imaginary part of their inner product is , giving the Robertson uncertainty principle
The canonical commutation relation gives . Retaining the real part of the same inner product gives the stronger Robertson-Schrödinger uncertainty relation, including a covariance term. These are constraints on the preparation of a quantum state, not simply statements about a poorly calibrated instrument.
A sequential spin one-half example makes the change in statistics explicit. Prepare . An immediate measurement is certainly positive. If an measurement is inserted first, its outcomes each have probability and leave states . Each then yields either result with probability , so the final positive fraction is . The change reflects projection onto incompatible spin eigenstates, even with ideal measuring apparatus. The theory of measurement in quantum mechanics allows more general state-update rules, but the operator description and the Born rule still constrain their probabilities.
The Born rule gives the required probability by integrating the probability density over the central interval. Put . For this infinite square well ground state,
Substitution of gives
This exceeds the interval's fraction of the box length because the ground state probability density is largest at the centre; it is not a uniform position distribution.
The photoelectric effect, black-body radiation and the Davisson–Germer experiment challenge different parts of a fully classical picture. Classical electromagnetic waves successfully describe propagation, interference and diffraction, while classical particles follow trajectories determined by forces. The difficulty is combining that picture with the observed exchange of energy between radiation and matter, the equilibrium distribution of radiation, and electron scattering. The three experiments expose the roles of discrete energy exchange and coherent matter waves.
In a photoelectric effect experiment, monochromatic light illuminates a metal cathode in vacuum and a second electrode collects emitted electrons. Varying the collecting voltage measures a photocurrent; reversing it until collection ceases determines the stopping potential. The observations distinguish two controls: at fixed frequency above threshold, increasing light intensity increases the emission rate, whereas the largest emitted kinetic energy is determined mainly by frequency. There is a material-dependent photoelectric threshold frequency, and emission above threshold does not require the long charging-up delay predicted by a simple picture of gradual classical energy accumulation at low intensity.
A classical wave carries continuously distributed energy, with intensity proportional to squared field amplitude. On a fully classical absorption picture, increasing intensity would be expected to increase the energy delivered to an electron, and sufficiently long exposure could accumulate the escape energy even below the observed threshold. It does not naturally produce the measured universal straight-line relation between stopping potential and light frequency. In 1905, Albert Einstein instead treated light-energy transfer as localized quanta. His argument distinguished the fastest escaping electrons from electrons losing energy before escape.[ref]
In the single-photon regime, conservation of energy gives the Einstein photoelectric equation
where is the surface work function. The photon supplies energy ; the escape cost is paid first, and the remainder sets the upper electron-energy edge. Increasing intensity at fixed frequency increases the number of available photons, so it raises current without raising this edge. Below , one photon cannot pay the escape cost. In an actual measurement, stable surface preparation, suppression of unwanted higher-frequency light, and the photoelectric contact-potential correction are needed to test the slope reliably. Robert Andrews Millikan's experiment used selected mercury spectral lines, freshly exposed metal surfaces and an electrometer to make such a quantitative test.[ref] The interpretation is for weak single-photon illumination; multiphoton photoemission at sufficiently intense fields is a different regime.
Black-body radiation tests equilibrium physics rather than the escape of individual electrons. A small aperture in an isothermal absorbing cavity approximates an ideal blackbody: radiation entering the hole undergoes repeated interactions with the walls, and the equilibrium spectrum depends on temperature rather than wall material. A spectrally resolving detector outside the aperture measures how emitted power varies with frequency or wavelength. Experimentally the spectrum has a finite peak, is strongly suppressed at short wavelengths, shifts toward shorter wavelengths when the cavity is heated, and has integrated emission proportional to .
For a large cavity, the electromagnetic mode density in a box, including two independent transverse polarizations, is per volume per unit frequency. The classical equipartition theorem assigns mean energy to each mode, leading to the Rayleigh-Jeans law
This agrees at low frequencies but diverges as frequency increases; integrating it over all frequencies gives infinite energy density at any nonzero temperature. This is the ultraviolet catastrophe, a failure of classical equipartition applied to the electromagnetic modes.
Max Planck's essential modification was that energy at a frequency is exchanged in units . In a modern oscillator description, the thermal excitation levels are , . Using the Boltzmann distribution and summing a geometric series gives
Multiplying by the mode density yields Planck's law for the spectral energy density,
When , expansion of the denominator recovers the classical law. When , the large excitation cost suppresses occupancy exponentially, removing the divergence. Its integral gives the Stefan–Boltzmann law, while its peak gives Wien's displacement law. Thus quantization repairs the spectral shape, total emission and temperature dependence together. The displayed thermal energy excludes the oscillator's temperature-independent zero-point energy.
The Davisson–Germer experiment supplies the complementary evidence that matter cannot always be treated as classical particles with definite scattering trajectories. In 1927, Clinton J. Davisson and Lester Halbert Germer sent a narrow, accelerated electron beam normally onto a single nickel crystal in vacuum. A movable collector measured the current of scattered electrons as direction and accelerating voltage were varied; a retarding potential selected electrons retaining approximately the incident energy. Sharp angular beams depended on crystal orientation and beam energy, with a prominent feature near and detector colatitude . These are scattering directions and currents, not photographs of electron paths.[ref]
The de Broglie wavelength predicts
At , this gives , comparable to atomic spacings. A crystalline arrangement supplies regularly spaced scattering sites, so scattered probability amplitudes can add constructively in selected directions. For a suitable family of crystal planes, Bragg's law expresses the condition as , with measured relative to those planes. The detector colatitude is not automatically this angle. The measured angular structure and its variation with electron momentum are described by electron diffraction with the de Broglie wavelength. A classical point-particle deflection model has no phase wavelength and does not supply that interference condition.
The common quantum account preserves the successes of wave propagation and particle detection while changing what is quantized. Photons exchange energy in frequency-dependent units; a thermal distribution of those excitations gives the blackbody spectrum. Electrons have a wavefunction whose amplitudes interfere on scattering from a crystal, while detection transfers localized charge. The Born rule turns squared amplitudes into event probabilities. These results invalidate a fully classical description of matter and radiation; the photoelectric energy law alone does not establish every property of a quantized electromagnetic field, but the three phenomena together provide complementary evidence for the quantum description.
The Born rule uses the squared modulus of the wavefunction, not its real part. Write . Then
Wavefunction normalization requires
Integrating the probability density over the required interval gives the dimensionless probability
Thus approximately of position measurements fall in this interval.