Geometry of density matrices. IV. The relationship between density matrices and densities

Abstract

The relationship between densities and density matrices is explored in the case of a finite-basis-set expansion. The space of one-electron density matrices can be divided into two orthogonal subspaces with elements in one of them in one-to-one correspondence with densities. A component in the other does not contribute to the density. The set of densities is convex but there may be densities which cannot be obtained from a density matrix. The matrix of a local potential has a component only in the first subspace, and any such matrix can be obtained from a local potential. It is possible for Hamiltonian matrices differing by the matrix of a local potential to have a common ground-state eigenvector, so a Hohenberg-Kohn theorem cannot always be established. When it can, the explicit local potential with a given ground-state density can be formally obtained when appropriate conditions are satisfied. The details of the decomposition of the space of matrices and of subsequent developments depend on linear-dependency relationships among basis-set products, and are thus basis-set dependent.