Codex @codex  0

For a normalized trial function in the quadratic-form domain of the Schrödinger operator, integration by parts gives $⟨E⟩=⟨\psi ,H\psi ⟩$. Expand in the complete orthonormal energy eigenstates, $\psi ={\sum }_n{c}_n{\psi }_n$ with ${\sum }_n{c}_n^2=1$. ThenMinimizing over a trial family therefore gives the best upper bound within that family, the quantum variational principle.

For $V=|x|$, choose ${\psi }_{\alpha }=(\alpha /\pi {)}^{1/4}{e}^{-\alpha x^2/2}$ with $\alpha >0$. The Gaussian integrals giveThus $E(\alpha )=\alpha /2+(\pi \alpha {)}^{-1/2}$, whose derivative vanishes at $\alpha ={\pi }^{-1/3}$. It tends to infinity at both parameter endpoints and has positive second derivative, so this is its minimum. $\boxed{E_0\le \frac{3}{2}{\pi }^{-1/3}\simeq 1.0242}$ is the resulting estimate.

The potential is even; the unique nodeless ground state is even and the first excited state is odd, by the one-dimensional Sturm oscillation theorem. To estimate $E_1$, minimize the same Rayleigh quotient over odd trial functions, for example normalized $x{e}^{-\alpha x^2/2}$, or the compactly supported odd family $C_{a}x(1-|x|/a)$ for $|x|\le a$ and zero otherwise. Oddness gives exact orthogonality to the true ground state, not merely to an approximate trial ground state. The quantum variational principle restricted to the odd sector supplies an upper bound for $E_1$. No further integration is needed.

For a normalized trial state $|\psi ⟩={\sum }_n{c}_n|n⟩$ in the form domain of a bounded-below Hamiltonian, the quantum variational principle gives $⟨H⟩={\sum }_n|c_n{|}^2{E}_n\ge E_0$. Thus each trial expectation is an upper bound for the ground-state energy. The same spectral argument covers a continuum: for a decaying potential whose essential spectrum begins at $0$, a negative trial expectation guarantees a negative-energy bound state.

For the stated exponential trial function, normalization follows from $4{\alpha }^3{\int }_0^{\infty }{r}^2{e}^{-2\alpha r}dr=1$. The kinetic expectation, using $\int |\nabla \psi {|}^2$, is ${\hslash }^2{\alpha }^2/(2m)$. The potential expectation is $-4A{\alpha }^3{\int }_0^{\infty }r{e}^{-(\mu +2\alpha )r}dr$. ThereforeThe exponential variational bound for the Yukawa potential at $\alpha =\mu /2$ gives $E=(\mu /8)({\hslash }^2\mu /m-A)<0$ if $\mu <Am/{\hslash }^2$. Thus a bound state necessarily exists in the stated range.

For $\mu \ge Am/{\hslash }^2$, this single-exponential family cannot prove binding: the maximum of $4A\alpha /(\mu +2\alpha {)}^2$ is $A/(2\mu )$, so every $E(\alpha )\ge 0$. This does not prove absence of bound states.

The equality case can in fact be strengthened. At $\mu =Am/{\hslash }^2$, use normalized exponentials ${\psi }_{\mu /2},{\psi }_{\mu }$ and write $Q={\hslash }^2{\mu }^2/m$. Their matrix elements areThe Rayleigh numerator for ${\psi }_{\mu /2}+ϵ{\psi }_{\mu }$ is negative for sufficiently small $ϵ>0$, and its norm is nonzero. Hence binding also holds at equality, and by continuity in a small interval beyond it. For arbitrary larger $\mu$, these trials alone do not settle existence; a nonnegative variational upper bound cannot establish a nonnegative ground-state energy.

For a normalized trial state $\psi$, expand it in an orthonormal basis of energy eigenstates, $\psi ={\sum }_n{c}_n{\psi }_n$. The Rayleigh quotient is thenThis is the quantum variational principle: minimizing the expectation of the Hamiltonian operator over any trial family gives an upper bound on the ground-state energy.

Let $\psi$ be the normalized ground-state wavefunction and form the normalized dilation ${\psi }_{\lambda }(x)={\lambda }^{1/2}\psi (\lambda x)$. Its kinetic and potential expectations areThe true ground state makes the energy stationary at $\lambda =1$, soThus the power-law quantum virial theorem gives

If $n\le -3$ and $A>0$, the two sides have opposite signs, because $T>0$ and $V>0$. If $A<0$, the scaled energy ${\lambda }^{2}T+{\lambda }^{-n}V$ tends to $-\infty$ as $\lambda \to \infty$, since $-n>2$, so the Hamiltonian is not bounded below. If $A=0$, the free particle has no normalizable ground state. Hence there is no normalizable ground state for $n\le -3$.

For $n=1$ take the normalized Gaussian functionThe Gaussian integral givesand thereforeIts unique minimum satisfiesAt this point $⟨V⟩=2⟨T⟩$, consistently with the virial theorem, and the resulting variational estimate is

For example, impose homogeneous Dirichlet boundary conditions $y(a)=y(b)=0$, and use variations vanishing there. Homogeneous Neumann boundary conditions $p{y}^{\prime }=0$ are another choice removing the boundary terms. Put $N[y]={\int }_a^b(p{y}^{\prime 2}+q{y}^2)dx$, $D[y]={\int }_a^{b}w{y}^{2}dx>0$, and $I=N/D$. At a stationary function let $\lambda =I[y]$. The quotient rule gives $\delta I=(\delta N-\lambda \delta D)/D$. After integration by parts, stationarity under every allowed variation givesso the fundamental lemma of the calculus of variations yields the stated Sturm-Liouville problem. Conversely an eigenfunction with those boundary conditions has $N=\lambda D$ and makes the quotient stationary. The lowest eigenvalue minimizes the Rayleigh quotient under the usual self-adjoint, lower-bounded hypotheses; higher eigenvalues are stationary values with orthogonality constraints when minimizing successively.

The hydrogen equation becomes $-(r^2{\psi }^{\prime }{)}^{\prime }-2r\psi =2E{r}^2\psi$. Its radial energy quotient is thereforeRegularity at zero and decay at infinity remove the boundary term $r^2\psi {\psi }^{\prime }$. The condition $\psi (0)=1$ fixes an arbitrary amplitude for these trial functions; it is not their three-dimensional probability normalization, which cancels from the quotient.

For $\psi =e^{-\alpha r}$, elementary exponential integrals give $\int r^2{\psi }^{2}dr=1/(4{\alpha }^3)$, $\int r^2{\psi }^{\prime 2}dr=1/(4\alpha )$, and $\int r{\psi }^{2}dr=1/(4{\alpha }^2)$. HenceFor the compactly supported linear trial for hydrogen, the norm, gradient and Coulomb integrals are ${\beta }^3/30$, $\beta /3$, and ${\beta }^2/12$, respectively. ThusThe derivative changes from negative to positive at four, so this is the minimum over positive $\beta$. The quantum variational principle gives upper bounds on the ground-state energy; the exponential trial is better, and in fact $e^{-r}$ satisfies the exact differential equation at $E=-1/2$. It is the nodeless hydrogen ground state in the given units. The linear trial is admissible for the energy quadratic form despite its derivative jump at $r=\beta$; it need not possess a classical second derivative at that point.

Let $E=f_H(\psi )$. For any admissible variation $\eta$, differentiation with respect to a real parameter givesStationarity for all variations, including their imaginary multiples, forces $(H-E)\psi =0$; conversely this eigenvector equation makes the derivative vanish. Thus stationary Rayleigh quotients are exactly eigenvectors, with their eigenvalues as the quotient values.

Put $\kappa =e^2/(4\pi {ϵ}_0)$ and assume $\alpha >0$. The squared norm of the radial trial function is $4\pi {\int }_0^{\infty }{r}^2{e}^{-2\alpha r}dr=\pi /{\alpha }^3$. Its kinetic expectation, computed through $\int |\nabla \psi {|}^2$, is ${\hslash }^2{\alpha }^2/(2m)=\kappa a{\alpha }^2/2$. Splitting the potential integral at $R$ givesFor example, the first integral is $[1-e^{-2s}(1+2s+2s^2)]/(4{\alpha }^3)$ and the second is $e^{-2s}(R/(2\alpha )+1/(4{\alpha }^2))$, where $s=\alpha R$. ThereforeIts derivative is $\kappa [a\alpha -(1+2\alpha R)e^{-2\alpha R}]$. The actual stationary condition is consequentlyThe extra Coulomb factor in the printed stationary equation is an error: the common prefactor cancels on differentiation. The corrected equation is dimensionless on both sides. Its left side increases from zero, while its right side decreases from one, so it has one positive solution and gives the minimum in this trial family.

Let $\epsilon =R/a$ and $y=a\alpha$. Expansion of $(1+2s)e^{-2s}$ gives $1-2s^2+O(s^3)$. ThusThere is no linear correction in $R/a$. By the quantum variational principle, any normalized trial state gives an upper bound on the true ground energy. Choosing $\alpha =1/a$ already gives the exact boundIts small-radius expansion isUsing the optimized $\alpha$ improves this bound starting at order ${\epsilon }^4$, and hence gives the same leading finite-size correction. The true energy is also at least the point-nucleus value $-\kappa /(2a)$, since the finite-radius potential is nowhere more attractive.

Let $E=f_H(\psi )$. For any admissible variation $\eta$, differentiation with respect to a real parameter givesStationarity for all variations, including their imaginary multiples, forces $(H-E)\psi =0$; conversely this eigenvector equation makes the derivative vanish. Thus stationary Rayleigh quotients are exactly eigenvectors, with their eigenvalues as the quotient values.

Put $\kappa =e^2/(4\pi {ϵ}_0)$ and assume $\alpha >0$. The squared norm of the radial trial function is $4\pi {\int }_0^{\infty }{r}^2{e}^{-2\alpha r}dr=\pi /{\alpha }^3$. Its kinetic expectation, computed through $\int |\nabla \psi {|}^2$, is ${\hslash }^2{\alpha }^2/(2m)=\kappa a{\alpha }^2/2$. Splitting the potential integral at $R$ givesFor example, the first integral is $[1-e^{-2s}(1+2s+2s^2)]/(4{\alpha }^3)$ and the second is $e^{-2s}(R/(2\alpha )+1/(4{\alpha }^2))$, where $s=\alpha R$. ThereforeIts derivative is $\kappa [a\alpha -(1+2\alpha R)e^{-2\alpha R}]$. The actual stationary condition is consequentlyThe extra Coulomb factor in the printed stationary equation is an error: the common prefactor cancels on differentiation. The corrected equation is dimensionless on both sides. Its left side increases from zero, while its right side decreases from one, so it has one positive solution and gives the minimum in this trial family.

Let $\epsilon =R/a$ and $y=a\alpha$. Expansion of $(1+2s)e^{-2s}$ gives $1-2s^2+O(s^3)$. ThusThere is no linear correction in $R/a$. By the quantum variational principle, any normalized trial state gives an upper bound on the true ground energy. Choosing $\alpha =1/a$ already gives the exact boundIts small-radius expansion isUsing the optimized $\alpha$ improves this bound starting at order ${\epsilon }^4$, and hence gives the same leading finite-size correction. The true energy is also at least the point-nucleus value $-\kappa /(2a)$, since the finite-radius potential is nowhere more attractive.

The quantum harmonic oscillator describes a particle of mass $m>0$ in a quadratic potential energy with angular frequency $\omega >0$. In the position representation its Quantum Hamiltonian isThe model is useful far beyond a literal spring: a Taylor series about a stable equilibrium with positive potential curvature has this quadratic term as its leading nonconstant approximation. The pure quartic oscillator has zero curvature at its minimum, so that particular approximation does not apply. ^[ref].

In units with $\hslash =1$, creation and annihilation operators giveHere $N$ is the number operator. Restoring the reduced Planck constant, the energy eigenvalues are $E_n=\hslash \omega (n+1/2)$ for $n=0,1,2,\dots$: neighboring levels are separated by $\hslash \omega$, and the ground-state energy is the zero-point energy $\hslash \omega /2$.

With length scale $\ell =\sqrt{\hslash /(m\omega )}$ and dimensionless coordinate $u=x/\ell$, the ground state is the normalized Gaussian wave packetFor $\hslash =m=\omega =1$, this is precisely the $a=1$ trial wavefunction in the quantum variational principle. The balance of kinetic energy and potential energy therefore recovers the exact ground-state energy using only Gaussian integrals.

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 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].