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For any nonzero state, the Rayleigh quotient isExpand $|\psi ⟩={\sum }_n{c}_n|{\psi }_n⟩$ in normalized energy eigenstates. ThenBecause the ground state is unique, equality holds exactly when all coefficients except $c_0$ vanish. Thus the Rayleigh-Ritz variational principle gives its minimum at the ray of $|{\psi }_0⟩$.

For the proposed exact state, write $\tilde{\psi }=e^{-\beta x^n}$. Its logarithmic derivatives giveThe stationary Schrödinger equation, after multiplication by $2m/{\hslash }^2$, isMatching the highest power requires $2n-2=6$, so $n=4$, and cancellation of $x^6$ requires $16{\beta }^2=1$. Normalizability selects $\beta =1/4$. Then $12\beta =3$ also cancels the quadratic term, leaving $\epsilon =2$. ThereforeThis is the exact ground state of a solvable sextic potential candidate $e^{-x^4/4}$.

For the Gaussian trial state ${\psi }_{\alpha }=e^{-\alpha x^2/2}$, normalization cancels from the quotient. With respect to the probability density proportional to $e^{-\alpha x^2}$,HenceThe stationary equation isWriting $z={\alpha }^2$, the quadratic has exactly one positive root,Since the quotient tends to infinity as $\alpha \downarrow 0$ or $\alpha \to \infty$, this is the unique global minimizer. ThusUsing the stationary equation to replace $15/(8{\alpha }_{\ast }^3)$ by ${\alpha }_{\ast }/6+1/(2{\alpha }_{\ast })$ gives the best estimateThis is the Gaussian variational estimate for a solvable sextic potential.

The exact eigenfunction $e^{-x^4/4}$ is positive and has no nodes. The nodeless theorem for a one-dimensional ground state therefore identifies it as the true ground state, with dimensionless energy $2$. The variational value is consistent: since ${\alpha }_{\ast }^2>3/2$,so $E_0^{\ast }>{\hslash }^2/m=E_0$, as every trial-state upper bound must satisfy.

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].