Variational derivation of density functional theory

Abstract

It is shown here that Kohn-Sham equations cannot be derived from Hohenberg-Kohn theory without an additional postulate. Assuming that a functional derivative with respect to total electron density exists leads in general to a theory inconsistent with the exclusion principle. A mathematically and physically correct variational theory of the Kohn-Sham model can be developed using functional derivatives with respect to orbital densities. These partial (Gâteaux) derivatives can be constructed explicitly from general N-electron theory and are defined throughout the orbital Hilbert space. This theory is consistent with the local density approximation (LDA), but does not in general imply multiplicative local exchange-correlation potentials. Progress beyond the LDA in condensed-matter physics requires development of methodology for nonlocal exchange and correlation potentials.