Generalized density functional theories using the k-electron densities: Development of kinetic energy functionals

Abstract

Several explicit formulas for the kinetic energy of a many-electron system as a functional of the k-electron density are derived, with emphasis on the electron pair density. The emphasis is on general techniques for deriving approximate kinetic energy functionals and features generalized Weisacker bounds and methods using density-matrix reconstruction. Adapting results from statistical mechanics, a hierarchy of equations is derived that links electron pairs, triplets, quadruplets, etc.; this may be used to derive more accurate approximations. Several methods for defining the exact kinetic energy functional are presented, including the generalizations of the Levy and Lieb formulations of density-functional theory. Together with N-representability constraints on the k-density, this paper provides the basis for “generalized density functional theories” based on the electron pair density. There are also implications for conventional density-functional theory, notably regarding the development of more accurate density functionals for the kinetic energy.