Kinetic and electron-electron energies for convex sums of ground state densities with degeneracies and fractional electron number.
Properties of exact density functionals provide useful constraints for the development of new approximate functionals. This paper focuses on convex sums of ground-level densities. It is observed that the electronic kinetic energy of a convex sum of degenerate ground-level densities is equal to the convex sum of the kinetic energies of the individual degenerate densities. (The same type of relationship holds also for the electron-electron repulsion energy.) This extends a known property of the Levy-Valone Ensemble Constrained-Search and the Lieb Legendre-Transform refomulations of the Hohenberg-Kohn functional to the individual components of the functional. Moreover, we observe that the kinetic and electron-repulsion results also apply to densities with fractional electron number (even if there are no degeneracies), and we close with an analogous point-wise property involving the external potential. Examples where different degenerate states have different kinetic energy and electron-nuclear attraction energy are given; consequently, individual components of the ground state electronic energy can change abruptly when the molecular geometry changes. These discontinuities are predicted to be ubiquitous at conical intersections, complicating the development of universally applicable density-functional approximations.
Department of Chemistry, Duke University, Durham, North Carolina 27708, USA.
Mel
M
Levy
Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario, Canada.
James S M
JS
Anderson
Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario, Canada.
Farnaz Heidar
FH
Zadeh
Department of Chemistry and Chemical Biology, McMaster University, Hamilton, Ontario, Canada.
Paul W
PW
Ayers