Approximately Self-Consistent Ensemble Density Functional Theory: Toward Inclusion of All Correlations

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Embargoed until: 2021-11-10
Author(s)
Gould, T
Griffith University Author(s)
Year published
2020
Metadata
Show full item recordAbstract
Recent theory developments in ensemble density functional theory (EDFT) promise to bring decades of work for ground states to the practical resolution of excited states, provided newly discovered “density-driven correlations” can be dealt with and adequate effective potentials can be found. This Letter introduces simple theories for both and shows that EDFT using these theories outperforms ΔSCF DFT and time-dependent DFT for low-lying gaps in most of the small atoms and molecules tested, even when all use the same density functional approximations. It thus establishes EDFT as a promising tool for low-cost studies of low-lying ...
View more >Recent theory developments in ensemble density functional theory (EDFT) promise to bring decades of work for ground states to the practical resolution of excited states, provided newly discovered “density-driven correlations” can be dealt with and adequate effective potentials can be found. This Letter introduces simple theories for both and shows that EDFT using these theories outperforms ΔSCF DFT and time-dependent DFT for low-lying gaps in most of the small atoms and molecules tested, even when all use the same density functional approximations. It thus establishes EDFT as a promising tool for low-cost studies of low-lying excited states and provides a clear route to practical EDFT implementation of arbitrary functional approximations.
View less >
View more >Recent theory developments in ensemble density functional theory (EDFT) promise to bring decades of work for ground states to the practical resolution of excited states, provided newly discovered “density-driven correlations” can be dealt with and adequate effective potentials can be found. This Letter introduces simple theories for both and shows that EDFT using these theories outperforms ΔSCF DFT and time-dependent DFT for low-lying gaps in most of the small atoms and molecules tested, even when all use the same density functional approximations. It thus establishes EDFT as a promising tool for low-cost studies of low-lying excited states and provides a clear route to practical EDFT implementation of arbitrary functional approximations.
View less >
Journal Title
Journal of Physical Chemistry Letters
Volume
11
Issue
22
Copyright Statement
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 2020 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpclett.0c02894
Subject
Physical Sciences
Chemical Sciences