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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.

The Rayleigh quotient measures the quadratic form of a self-adjoint operator per unit squared norm. For a nonzero vector $x$ and a finite-dimensional Hermitian matrix $A$,For a real symmetric matrix, replace the conjugate transpose $x^{\ast }$ by $x^T$. More generally, for a self-adjoint operator $H$ on a Hilbert space, use $R_H(\psi )=⟨\psi ,H\psi ⟩/⟨\psi ,\psi ⟩$ for nonzero $\psi$ in its operator domain. On an eigenvector it returns the exact eigenvalue. Multiplying the vector by any nonzero scalar leaves the quotient unchanged, so it measures a direction rather than a chosen length.

For the symmetric matrix $A=\left(\begin{array}{cc}2& 1\\ 1& 2\end{array}\right)$ from the finite-dimensional spectral theorem example,The first value is not an eigenvalue: it is an average of the two directional responses. To see every direction, write the unit vector $q(\theta )=\cos \theta e_{+}+\sin \theta e_{-}$ in the orthonormal eigenbasis. ThenThe largest value is $3$ along $e_{+}$; the smallest is $1$ along $e_{-}$. A direction halfway between them has quotient $2$. In the left panel, the color on the unit circle represents the quotient; in the right panel, the same values are plotted against the angle measured from $e_{+}$.

The Hermitian Rayleigh quotient range explains why this is useful: evaluating one trial vector gives an upper bound on the smallest eigenvalue and a lower bound on the largest one, without solving a characteristic polynomial. At an extreme eigenvector, a small angular error changes the quotient only quadratically. Near $e_{+}$ in this example, $3-R_A(q(\theta ))=2{\sin }^2\theta =2{\theta }^2+O({\theta }^4)$. This is the geometric reason for quadratic Rayleigh-quotient improvement for the power method and motivates the Rayleigh-Ritz method.

There is a concrete historical link with normal modes. In The Theory of Sound (1877), Volume I, Sections 88–89, Lord Rayleigh studies the period of a constrained trial vibration. He shows that the period has a stationary point at a normal mode and that a trial type bounds the longest natural period. These energy ratios are a mechanical setting for the modern Rayleigh quotient and generalized Rayleigh quotient; the book describes the result through vibration periods, rather than today's matrix notation.^[ref]

The Robertson-Schrödinger uncertainty relation keeps the real part discarded in the proof of the Robertson uncertainty principle. Write $A^{\prime }=A-⟨A⟩I$ and $B^{\prime }=B-⟨B⟩I$. Their quantum covariance is $C_{AB}=\mathrm{Re}⟨A^{\prime }\psi |B^{\prime }\psi ⟩$. On the same finite-moment and product operator domains used above, the Cauchy-Schwarz inequality givesFor position and momentum, form the real, symmetrized covariance matrixA larger coordinatewise product can therefore encode a tilted covariance ellipse, rather than a larger determinant. This explains why the equality case of the Heisenberg uncertainty relation is more restrictive than equality in the Robertson-Schrödinger uncertainty relation.

The Robertson uncertainty principle bounds the product of the standard deviations of two observables in the same quantum state. For a normalized pure state $|\psi ⟩$ and self-adjoint operators $A,B$, write their expectation values and variances asand similarly for $B$, where $I$ is the identity operator. The quantum uncertainties $\Delta A,\Delta B$ then obeyHere $[A,B]$ is the commutator, and every expectation value is taken in the same $|\psi ⟩$. These standard deviations describe the outcome spreads when $A$ and $B$ are measured on separate ensembles prepared in that same quantum state. They are not instrument errors or the change caused by a preceding measurement in quantum mechanics. The definition and bound are developed in Barton Zwiebach, Uncertainty Principle and Compatible Observables, 2013, §§1–2.

For unbounded self-adjoint operators, the operator domains matter. Assume $\psi \in D(A)\cap D(B)$, so that both second moments are finite; $⟨A^2⟩$ here means the second moment of the measured probability distribution, equal to $\Vert A\psi {\Vert }^2$, even if $A^2\psi$ is undefined. To use the displayed operator commutator, also assume $\psi \in D(AB)\cap D(BA)$. Without these product-domain assumptions, the always meaningful version on $D(A)\cap D(B)$ uses $|\mathrm{Im}⟨A\psi |B\psi ⟩|$ as its right-hand side. These qualifications prevent a formal commutator identity from being applied to an inadmissible quantum state.

The brief proof is Cauchy-Schwarz inequality applied to $u=(A-⟨A⟩I)\psi$ and $v=(B-⟨B⟩I)\psi$:The final equality uses self-adjointness and the product-domain assumptions. Thus a geometric statement about inner products becomes a constraint on experimental spreads. For nonzero $\Delta A,\Delta B$, equality requires $u,v$ to be proportional with a purely imaginary proportionality factor; the equality case of the Heisenberg uncertainty relation turns this condition into a Gaussian wave packet.

The bound is useful because computing a single commutator and its expectation value can constrain two entire outcome distributions. Its right-hand side depends on the quantum state: the spin uncertainty state dependence example gives both a positive saturated bound and a zero bound for the same noncommuting observables. Robertson's paper, titled "The Uncertainty Principle", appeared on 1 July 1929 in Physical Review, volume 34, starting at page 163. ^[ref].

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.

A densely defined operator $T$ on a Hilbert space is self-adjoint when it equals its adjoint operator, including equality of their operator domains:For a bounded linear operator defined on the whole Hilbert space, this is equivalent tofor all vectors $v,w$. For an unbounded self-adjoint operator, the domain condition is essential: the inner-product identity on $D(T)$ alone gives only a symmetric operator.

A densely defined operator $T$ on a Hilbert space is symmetric whenEquivalently, $T$ agrees with its adjoint operator on $D(T)$, while $D(T^{\ast })$ may be larger. A self-adjoint operator additionally requires equality of these operator domains.

For a time-independent Hamiltonian operator $H$, an energy eigenstate satisfiesFor a one-dimensional particle of mass $m$ in a real potential energy $U(x)$,Its full time-dependent wavefunction is $\Psi (x,t)=\psi (x)e^{-iEt/\hslash }$: substitution in the Schrödinger equation checks both the minus sign and the factor $\hslash$. Thus an energy eigenstate has stationary position probability density, even though its quantum phase evolves. The boundary conditions and operator domain are part of this eigenvalue problem, selecting physically allowed solutions; the infinite square well and Radial Schrodinger equation for the hydrogen atom give complementary confined examples.

For a complete discrete orthonormal basis of energy eigenstates, linearity gives $\Psi (x,t)={\sum }_n{c}_n{\psi }_n(x)e^{-i{E}_{n}t/\hslash }$, with ${\sum }_n|c_n{|}^2=1$. Cross terms in $|\Psi {|}^2$ oscillate at angular frequencies $(E_n-E_m)/\hslash$. A continuous spectrum requires the corresponding spectral integrals; for a free particle on the whole line, individual plane waves are generalized eigenfunctions, and a normalized Gaussian wave packet is their integral quantum superposition. Adding a spatially constant real $C$ to $U$ shifts every energy eigenvalue by $C$ and multiplies the full state by $e^{-iCt/\hslash }$, a global phase; energy differences, position probabilities and probability current are unchanged.

A time-independent Hamiltonian evolves a state by the unitary operator $U(t)=e^{-iHt/\hslash }$.

For a closed quantum system, unitary time evolution changes a quantum state through a unitary operator, preserving norms and inner products. For a time-independent self-adjoint Hamiltonian operator $H$, choose the initial time as zero:Here $\hslash =h/(2\pi )$ is the reduced Planck constant. The same $U(t)$ acts on every initial quantum state; it depends on the Hamiltonian operator and elapsed time, rather than the chosen preparation.^[ref]

The self-adjointness of $H$ makes the exponential a unitary operator. In finite dimension, conjugating its matrix exponential givesThe two exponents commute because both are multiples of $H$. Hence, for any two initial vectors,This short proof explains why normalization survives, why orthogonality of initial vectors survives, and why the transition probability between two states evolved by the same $U$ is unchanged. It does not require that a fixed measurement in quantum mechanics have time-independent probabilities: its measurement basis need not move with the quantum states.

For an unbounded self-adjoint operator, define the exponential through the spectral theorem, rather than assuming that its power series acts on every vector. It is a unitary operator on the entire Hilbert space; the strong Schrödinger equation holds for initial vectors in the operator domain $D(H)$. For a density operator, unitary time evolution reads $\rho (t)=U(t)\rho (0)U(t{)}^{†}$. It preserves eigenvalues and purity of a density operator, but can change its entries in a fixed basis.

The useful distinction is between conserving total probability and conserving each measurement's probabilities. A fixed energy spectrum supplies different ticking rates for different probability amplitudes. Their relative quantum phases can move the Bloch vector and create quantum interference even while every energy eigenstate population stays fixed. Qubit precession under a constant Hamiltonian makes this visible; Ramsey interferometry converts the accumulated relative quantum phase into a population difference that a simple readout can detect.

The variational method estimates the lowest energy of a Quantum Hamiltonian by choosing a trial wavefunction, evaluating its energy, and optimizing the trial parameters. It uses the quantum variational principle, the Rayleigh-Ritz variational principle expressed for quantum states. Let $H$ be a self-adjoint operator bounded below, and define $E_0=\inf \sigma (H)$, the bottom of its spectrum. Every normalized admissible trial quantum state satisfiesWhen $E_0$ is an energy eigenvalue, it is the ground-state energy; equality holds precisely for a quantum state in the ground-state subspace. Otherwise the bottom of the spectrum need not be attained by any normalizable wavefunction.

Admissible means finite form energy. Choose a real $b\le E_0$ and use the shifted quadratic form of a positive quantum Hamiltonian:The form domain $Q(H)$ is independent of this choice of $b$ and can be larger than the operator domain $D(H)$. For $\psi \in D(H)$, $E_{\psi }=⟨\psi ,H\psi ⟩$ is the usual expectation value; for nonzero unnormalized trials, divide $q_H[\psi ]$ by $\Vert \psi {\Vert }^2$ to get the form version of the Rayleigh quotient. See the quantum variational principle for the general domain justification.

Thus each trial energy is an upper bound on $E_0$, and minimizing within a trial family improves that upper bound. It is not a lower bound on $E_0$. The Gaussian variational energy for the harmonic oscillator reaches $E_0=1/2$ because its family contains an exact ground state. The exact variational solution in a two-level system makes the equality condition visible as vanishing excited-state probability amplitude.

The method is useful when solving the Schrödinger equation exactly is difficult but integrals of a trial wavefunction are tractable. Enlarging a trial family cannot increase its optimal energy, although an optimum need not be attained. The beauty is that even an imperfect trial gives a rigorous bound, provided its form energy is computed exactly: numerical integration errors require separate control. The Gaussian variational estimate for a solvable sextic potential provides an existing example beyond a quantum harmonic oscillator.

A short proof explains the direction. With a complete orthonormal eigenbasis of energy eigenstates, write $\psi ={\sum }_n{c}_n{\varphi }_n$, where $H{\varphi }_n=E_n{\varphi }_n$ and ${\sum }_n|c_n{|}^2=1$. ThenThis is a weighted mean of nonnegative energy differences; equality requires every occupied energy eigenstate to have energy $E_0$. ^[ref]. For continuous spectrum, the spectral theorem replaces the sum by an integral against the scalar spectral measure of $\psi$, with the same nonnegative integrand. This proves the bound without assuming an orthonormal eigenbasis exists.

The historical setting predates quantum mechanics: Rayleigh's The Theory of Sound, volume I, appeared in 1877, and Ritz's paper on solving variational problems of mathematical physics appeared in volume 135 of Crelle's journal, catalogued by its publisher as 1909, pp. 1–61. These are original works associated with the Rayleigh-Ritz method; the dates here identify the publications rather than assert priority. ^[ref]; ^[ref].