Electron Densities, Momentum Densities, and Density Matrices

Abstract

Abstract Relationships among electron coordinate-space and momentum densities and the one-electron charge density matrix or Wigner function are examined. A knowledge of either or both densities places constraints on possible density matrices. Questions are approached in the context of a finite-basis-set model problem in which density matrices are elements in a Euclidean vector space of Hermitian operators or matrices, and densities are elements of other vector spaces. The maps (called "collapse") of the operator space to the density spaces define a decomposition of the operator space into orthogonal subspaces. The component of a density matrix in a given subspace is determined by one density, both densities, or neither. Linear dependencies among products of basis functions play a fundamental role. Algorithms are discussed for finding the subspaces and constructing an orthonormal set of functions spanning the same space as a linearly dependent set. Examples are presented and additional investigations suggested.