Single Excitation Energies Obtained from the Ensemble “HOMO–LUMO Gap”: Exact Results and Approximations

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Gould, Tim
Hashimi, Zahed
Kronik, Leeor
Dale, Stephen G
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2022
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Abstract

In calculations based on density functional theory, the "HOMO-LUMO gap"(difference between the highest occupied and lowest unoccupied molecular orbital energies) is often used as a low-cost, ad hoc approximation for the lowest excitation energy. Here we show that a simple correction based on rigorous ensemble density functional theory makes the HOMO-LUMO gap exact in principle and significantly more accurate in practice. The introduced perturbative ensemble density functional theory approach predicts different and useful values for singlet-singlet and singlet-triplet excitations, using semilocal and hybrid approximations. Excitation energies are similar in quality to time-dependent density functional theory, especially at high fractions of exact exchange. The approach therefore offers an easy-to-implement and low-cost route to robust prediction of molecular excitation energies.

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The Journal of Physical Chemistry Letters

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13

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10

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This document is the Postprint: Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry Letters, copyright 2022 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/acs.jpclett.2c00042

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Physical chemistry

Chemical sciences

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Chemistry, Physical

Nanoscience & Nanotechnology

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Gould, T; Hashimi, Z; Kronik, L; Dale, SG, Single Excitation Energies Obtained from the Ensemble “HOMO–LUMO Gap”: Exact Results and Approximations, The Journal of Physical Chemistry Letters, 2022, 13 (10), pp. 2452-2458

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