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

revised on 13.04.2018, 05:04 and posted on 13.04.2018, 14:38 by Tim Gould, Stefano Pittalis, Leeor Kronik
By studying the lowest excitations of an exactly solvable one-dimensional \SP{}{soft-Coulomb} 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 the 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.


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Griffith University



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in The Journal of Chemical Physics