Charge transfer excitations from exact and approximate ensemble Kohn-Sham theory

19 January 2018, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Paper providing a proof-of-principle that ensemble DFT can reproduce difficult charge transfer physics.

By studying the lowest excitations of an exactly solvable one-dimensional molecular model, we show that components of Kohn-Sham ensembles can be used to describe charge transfers. Furthermore, we compute the approximate excitation energies obtained by using thee exact ensemble densities in the recently formulated ensemble Hartree-exchange theory [Gould and Pittalis, Phys. Rev. Lett. 119, 243001 (2017)]. Remarkably, our results show that triplet excitations are accurately reproduced across a dissociation curve in all cases tested, even in systems where ground state energies are poor due to strong static correlations. Singlet excitations exhibit larger deviations from exact results but are still reproduced semi-quantitatively.

Keywords

EDFT
charge transfer
excitations
ensembles
Chemistry
Physics

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