“Ensemblization” of density functional theory

Abstract

Density functional theory (DFT) has transformed our ability to investigate and understand electronic ground states. In its original formulation, however, DFT is not suited to addressing (e.g.) degenerate ground states, mixed states with different particle numbers, or excited states. All these issues can be handled, in principle exactly, via ensemble DFT (EDFT). This Perspective provides a detailed introduction to and analysis of EDFT, in an in-principle exact framework that is constructed to avoid uncontrolled errors and inconsistencies that may be associated with ad hoc extensions of conventional DFT. In particular, it focuses on the “ensemblization” of both exact and approximate density functionals, a term that we coined to describe a rigorous approach that lends itself to the construction of novel approximations consistent with the general ensemble framework, applicable to practical problems where traditional DFT tends to fail or does not apply at all. In particular, symmetry considerations and ensemble properties are shown to enable each other in shaping a practical DFT-based methodology that extends beyond the ground state and, in doing so, highlights the need to look outside the standard ground state Kohn–Sham treatment.