 Solution

The quantum variational principle turns the ground-state problem into minimization of a Rayleigh quotient:The Hamiltonian must be a self-adjoint operator bounded below, and the nonzero trial state must have finite form energy. Expanding a normalized trial state in exact energy eigenstates gives $E[\psi ]={\sum }_n|c_n{|}^2{E}_n$, a weighted average no smaller than $E_0$. Equality requires support only in the ground-state eigenspace. The spectral version also accommodates continuous spectrum; a lowest normalizable eigenstate is not required merely to bound the spectral infimum.

The variational method chooses a trial family with the correct boundary conditions, fermionic exchange symmetry and other required quantum numbers, evaluates its energy and minimizes over its parameters. It gives an upper bound on ground-state energy. Enlarging a nested trial family can only improve or preserve its optimal bound. A low energy does not by itself establish a highly accurate wavefunction, especially near degeneracy; energy errors are second order in small admixtures orthogonal to a nondegenerate exact ground state.

For example, a normalized Gaussian trial for a one-dimensional quantum harmonic oscillator is ${\psi }_{\beta }=(\beta /\pi {)}^{1/4}{e}^{-\beta x^2/2}$, with $\beta >0$. Its energy isThe two terms balance kinetic localization cost against the potential cost of spreading out. This Gaussian variational energy for the harmonic oscillator happens to attain the exact answer because the family contains the exact ground state.

A trial expansion $\psi ={\sum }_j{c}_j{\chi }_j$ in a finite, possibly nonorthogonal basis gives the generalized eigenvalue problem $H\mathbf{c}=ES\mathbf{c}$, with $H_{ij}=⟨{\chi }_i|H|{\chi }_j⟩$ and $S_{ij}=⟨{\chi }_i|{\chi }_j⟩$. Its lowest Ritz value minimizes the quotient in that subspace. For excited states, the excited-state variational constraint imposes exact orthogonality to the lower eigenstates to obtain a corresponding upper bound; the Courant–Fischer min-max principle yields upper bounds for ordered Ritz eigenvalues from a common subspace. orthogonality only to an independently approximate ground state does not automatically provide an excited-state bound: residual true-ground-state contamination can lower the trial energy below the desired excited energy. Symmetry can impose exact orthogonality when the relevant states have different symmetry sectors.