Density-Driven Correlations in Many-Electron Ensembles: Theory and Application for Excited States

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Gould, Tim
Pittalis, Stefano
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2019
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Abstract

Density functional theory can be extended to excited states by means of a unified variational approach for passive state ensembles. This extension overcomes the restriction of the typical density functional approach to ground states, and offers useful formal and demonstrated practical benefits. The correlation energy functional in the generalized case acquires higher complexity than its ground state counterpart, however. Little is known about its internal structure nor how to effectively approximate it in general. Here we show that such a functional can be broken down into natural components, including what we call "state-" and "density-driven" correlations, with the former amenable to conventional approximations, and the latter being a unique feature of ensembles. Such a decomposition provides us with a pathway to general approximations that are able to routinely handle low-lying excited states. The importance of density-driven correlations is demonstrated, and an approximation for them is introduced and shown to be useful.

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Physical Review Letters

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123

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1

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© 2019 American Physical Society. This is the author-manuscript version of this paper. Reproduced in accordance with the copyright policy of the publisher. Please refer to the journal's website for access to the definitive, published version.

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Mathematical sciences

Physical sciences

Engineering

Science & Technology

Physics, Multidisciplinary

Physics

FRACTIONALLY OCCUPIED STATES

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Gould, T; Pittalis, S, Density-Driven Correlations in Many-Electron Ensembles: Theory and Application for Excited States, Physical Review Letters, 2019, 123 (1), pp. 016401:1-016401:6

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