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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].

Vector normalization converts a nonzero vector in a normed vector space into a unit vector. Absolute homogeneity of a norm givesThe direction is unchanged by multiplying by a positive real scalar. For $c>0$, $\Vert cv\Vert =c\Vert v\Vert$ and $\widehat{cv}=\hat{v}$; for a negative real scalar, $\widehat{cv}=-\hat{v}$. Thus $(3,4)$ and $(6,8)$ normalize to the same unit vector, while $(-3,-4)$ normalizes to its negative. This decomposition is useful for specifying a direction independently of a force, velocity or displacement magnitude.

In a complex normed vector space, a nonzero complex scalar $c$ instead gives $\widehat{cv}=(c/|c|)\hat{v}$. The remaining complex argument is not removed by normalization. For a pure quantum state, vectors differing only by this overall global phase represent the same physical state; vector normalization alone does not identify them.

The zero vector cannot be normalized this way. The construction also applies in a function space: an eigenfunction of a Sturm-Liouville problem can be scaled to unit weighted norm byThe positive weight $w$ specifies the weighted inner product. Multiplication by this nonzero constant preserves the eigenvalue equation and its homogeneous boundary conditions.

A joint electronic and vibrational quantum state of a molecule. In a product approximation its irreducible representation is the tensor product of group representations of the electronic and vibrational factors.

Use the leading nonrelativistic magnetic coupling for an electronic level with total angular momentum operator $\mathbf{J}$, and choose the $z$ axis along a uniform external magnetic field $\mathbf{B}=B\hat{\mathbf{z}}$, $B\ge 0$. Write its magnetic quantum number as $m_J$, so $J_z|J,m_J⟩=\hslash m_J|J,m_J⟩$. There are $2J+1$ possibilities from $-J$ to $J$. With Landé g-factor $g_J$, the first-order shift isHere $e>0$ is the magnitude of the electron electric charge, $m_e$ its mass, $h$ the Planck constant, and ${\mu }_B$ the Bohr magneton. Both $g_J$ and $m_J$ are dimensionless; with $B$ measured in tesla and ${\mu }_B$ in joules per tesla, $\Delta E$ is in joules. The photon frequency shift $\Delta {\nu }_{ul}$ is in hertz, not angular frequency; indices $u,l$ denote upper and lower levels. NIST states this weak-field convention and its orbital/spin assumptions explicitly.^[ref]

The sign follows directly from magnetic dipole potential energy. Within this electronic $J$ multiplet, the projected magnetic dipole moment is $\mathbf{\mu }=-g_J{\mu }_B\mathbf{J}/\hslash$. Therefore $H_Z=-\mathbf{\mu }\cdot \mathbf{B}$ has the displayed positive coefficient. Subtracting the shifts of the two levels and using photon energy $h{\nu }_{ul}=E_u-E_l$ gives the transition formula. For the orbital case, ${\mu }_B/h=e/(4\pi m_e)$ gives the same leading frequency spacing as the classical charged oscillator. This explains the historical sensitivity to charge divided by mass; the quantum state derivation here is modern.

“Weak” compares interaction energies: mixing with neighbouring fine structure levels must be small, so $J$ remains a useful quantum number. The formula keeps the term linear in $B$ and neglects quadratic shifts. It also omits hyperfine structure; if that is resolved and controls the coupling, the appropriate total electronic-plus-nuclear angular momentum and splitting factor must replace $J,g_J$. Weak compared with fine structure does not automatically mean weak compared with hyperfine structure.

A physicist.^[ref]

A white dwarf is a compact stellar remnant supported mainly by electron degeneracy pressure. Its ions carry most of the mass, while its electrons provide most of the supporting pressure. The Pauli exclusion principle makes compression fill quantum states with larger momenta; support therefore persists even when thermal motion becomes small. Cooling and hydrostatic equilibrium are separate questions: a white dwarf can radiate stored energy while retaining degeneracy support.

The surprising trend is that a more massive cold white dwarf is smaller. Its higher mass density raises the Fermi momentum, eventually requiring special relativity. The degenerate-electron pressure crossover explains why this response approaches a limiting stiffness and why the Chandrasekhar limit exists. Subrahmanyan Chandrasekhar's 1983 lecture develops this connection between quantum statistics, stellar structure and stellar evolution.^[ref]

A physicist.^[ref]

The drive can supply or extract work while the quantum state stays approximately fixed. For a differentiable bounded Hamiltonian operator, the Schrödinger equation givesThe state-evolution terms cancel, leaving the external drive's power. For a finite ideal step the change in mean energy is $⟨\psi |H_f-H_i|\psi ⟩$. Thus conservation of energy for a closed system with a time-independent Hamiltonian operator does not assert conservation of the driven subsystem's energy during switching.

Specify work operationally by two energy measurements: one before the switch and one after. For the prepared initial ground state, the first outcome is definite; the second samples the new Born rule probabilities. This protocol gives a distribution of measured energy differences, rather than generally the measurement distribution of the single operator $H_f-H_i$.^[ref]and henceFor ${\Delta }_i={\Delta }_f=\Delta$ and $\theta =\pi /3$, the work is $0$ or $\Delta$, with probabilities $3/4$ and $1/4$; its expectation is $\Delta /4$ and its variance is $3{\Delta }^2/16$. The initial mean energy $-\Delta /2$ becomes $-\Delta /4$. Using different initial and final scalar offsets would also shift the measured work; the displayed Hamiltonian operators fix that convention explicitly.

Zeeman splitting is the separation of energy levels or mode frequencies by a background magnetic field. In atomic physics, the magnetic field couples to a magnetic dipole moment, lifting quantum degeneracy. Transitions between the shifted quantum states can turn one spectral line into several. A split level and a split spectral line are different objects: the emitted photon measures the difference between two level energies, and the electric-dipole selection rule determines which differences appear.

The Stern-Gerlach experiment also probes magnetic dipole moments, through beam deflection in a magnetic field gradient. Here the readout is a spectral line.

The pattern makes an invisible magnetic field visible through spectroscopy. It also reveals angular momentum and magnetic dipole moments inside chemical atoms. Zeeman slowers exploit a changing resonance frequency to keep moving chemical atoms absorbing laser photons; a magneto-optical trap combines position-dependent shifts with electromagnetic polarization and laser cooling. Related mode shifts occur in Zeeman splitting of an antiferromagnetic spin wave.

For $M$ complete energy eigenstates of a one-particle Quantum Hamiltonian for identical noninteracting fermions, order their energies ${ϵ}_1\le \cdots \le {ϵ}_M$. At fixed particle number $0\le N\le M$, the Quantum Hamiltonian and the particle-number constraint areThe ground state occupies the $N$ lowest complete one-particle states. A short minimization argument suffices: moving an occupant from a higher energy to an empty lower energy decreases the total energy. This filling describes the ground state at temperature $T=0$; exclusion by itself also applies to excited quantum states and at positive temperature. The underlying thermal description is the Fermi-Dirac distribution.^[ref]

If the last occupied energy belongs to a group of $g$ one-particle states at the same energy and $q$ of them must be occupied, with all lower states filled, the ground state subspace has dimension $\left(\genfrac{}{}{0ex}{}{g}{q}\right)$. Exclusion does not select a particular basis or a particular quantum superposition in that subspace. The factor of two for an electron spatial orbital assumes both spin projections are included; a model restricted to one spin projection has only one state per spatial orbital. A magnetic field can split the degenerate energy levels, and interactions can change the lowest-energy electron configuration. Thus this finite noninteracting filling rule is not a complete prescription for interacting chemical atoms.

A physicist working on quantum information. Affiliation recorded at publication in 2018: University of Science and Technology of China, CAS Key Laboratory of Quantum Information.^[ref]