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A fermionic mode with canonical anticommutation relations $\{b,b^{†}\}=1$ has the symmetrically ordered Hamiltonian operator $H=\frac{E}{2}(b^{†}b-b{b}^{†})=E(b^{†}b-1/2)$. Its empty-state zero-point contribution is $-E/2$. A quantum harmonic oscillator with bosonic canonical commutation relations contributes $+E/2$ instead. For a Dirac field, sum over both particle and antiparticle modes and over spin: there are four independent oscillators per spatial momentum in four spacetime dimensions. Comparing bosonic and fermionic vacuum energies requires a common regularization in quantum field theory, matching degrees of freedom and a stated vacuum-energy subtraction convention.

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].

In the independent harmonic approximation, each diatomic molecule has one bond-stretching quantum harmonic oscillator with energies $(n+1/2)\hslash \omega$. Write $x=\hslash \omega /(k_{B}T)$. Its canonical partition function is $z=e^{-x/2}/(1-e^{-x})$, and differentiating its logarithm givesFor $T\ll \hslash \omega /k_B$, excitation is exponentially suppressed and the heat capacity tends to zero. At high temperature it tends to $N{k}_B$, one $k_B/2$ contribution from each quadratic kinetic and potential term. The zero-point energy does not contribute to the derivative with temperature. For a dilute gas whose rotations are already active, adding translation and rotation gives molar $C_V\simeq 5R/2$ before vibration is activated and $7R/2$ afterwards, provided dissociation and electronic excitations are negligible.

A vibrational partition function sums over molecular vibrational energy levels. A single quantum harmonic oscillator, with energies measured relative to its ground level and vibrational temperature ${\theta }_v=h\nu /k$, has $q_{\mathrm{vib}}=(1-e^{-{\theta }_v/T}{)}^{-1}$. Retaining its absolute zero-point energy multiplies this by $e^{-{\theta }_v/(2T)}$. That factor shifts the internal energy but contributes no entropy.

Zero-point motion is the nonzero quantum fluctuation of position and momentum in a system's ground state. For a quantum harmonic oscillator, the ground state has energy $\hslash \omega /2$ and nonzero position and momentum variances even at zero temperature. It does not represent a thermal mixture and need not carry entropy. The large zero-point motion of light helium atoms helps explain why helium can remain a liquid at low pressure even as temperature approaches absolute zero.