Brillouin's theorem and the Hellmann-Feynman theorem for Hartree-Fock wave functions

Abstract

It is shown that there is an intimate relation between the Hellmann-Feynman theorem and Brillouin's theorem. A more general form of Brillouin's theorem is provided, which applies to excited states of arbitrary symmetry and multiplicity. This new form leads to a simple proof of the Hellmann-Feynman theorem. This theorem is valid when all the orbitals that occur in the wave function are determined by a complete, and not a partial, variational procedure. Arguing in the opposite direction it is shown that the complete satisfaction of the generalized Brillouin's theorem provides an alternative scheme for obtaining the Hartree-Fock orbitals.