Information entropy as a measure of the correlation energy associated with the cumulant

Abstract

A linear relation is found between Jaynes entropy and the correlation energy associated with the cumulant for a correlated molecular system, as demonstrated in ${\mathrm{H}}_{2}$ and a water molecule. The relation modifies the Collins conjecture, in which the correlation energy is defined as the total energy difference with reference to the Hartree-Fock counterpart. The linear behavior is system dependent and shifts slightly on a different basis set. This correlation energy is extensive. For a system whose wave function can be expressed as the antisymmetrized product of orthogonal groups, the correlation energy is just the sum of the individual groups. The finding offers a convenient way to construct an approximate correlation energy functional in reduced density-matrix-functional theory, which may be used in large-scale molecular dynamics simulations and potential energy surface calculations where the molecular geometry needs to be frequently updated.