Individual Correlations in Ensemble Density Functional Theory: State- and Density-Driven Decompositions without Additional Kohn-Sham Systems

Abstract

Gould and Pittalis [Phys. Rev. Lett. 123, 016401 (2019)PRLTAO0031-900710.1103/PhysRevLett.123.016401 recently revealed a density-driven (DD) correlation energy that is specific to many-electron ensembles and must be accounted for by approximations. We derive in this Letter a general and simpler expression in terms of the ensemble weights, the ensemble Kohn-Sham (KS) orbitals, and their linear response to variations in the ensemble weights. As no additional state-driven KS systems are needed, its evaluation is greatly simplified. We confirm the importance of DD effects and introduce a direct and promising route to approximations.

Topics & Concepts