Analytic Construction of One-Electron Reduced Density Matrices from Electron Densities within Finite Basis Sets.

Abstract

We show how to construct analytically all one-electron reduced density matrices (1-RDMs) compatible with a given electron density within a finite basis set, provided that the density is specified as a symmetric quadratic form in terms of the basis functions. Contrary to the current belief, exact linear dependencies in the basis function products assist, rather than hinder, such constructions. By applying the N-representability conditions to the analytically reconstructed 1-RDMs, one can perform a constrained search over physically acceptable 1-RDMs that yield a given finite-basis-set density. The discussion is illustrated with worked-out examples.