Describing strong correlation with fractional-spin correction in density functional theory

Su, Neil Qiang; Li, Chen; Yang, Weitao

doi:10.1073/pnas.1807095115

Title: Describing strong correlation with fractional-spin correction in density functional theory

Journal Article · Mon Sep 10 00:00:00 EDT 2018 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1807095115· OSTI ID:1469268

^[1]; Li, Chen ^[1]; Yang, Weitao ^[2]

Department of Chemistry, Duke University, Durham, NC 27708,
Department of Chemistry, Duke University, Durham, NC 27708,, Key Laboratory of Theoretical Chemistry of Environment, School of Chemistry and Environment, South China Normal University, Guangzhou 510006, China

An effective fractional-spin correction is developed to describe static/strong correlation in density functional theory. Combined with the fractional-charge correction from recently developed localized orbital scaling correction (LOSC), a functional, the fractional-spin LOSC (FSLOSC), is proposed. FSLOSC, a correction to commonly used functional approximations, introduces the explicit derivative discontinuity and largely restores the flat-plane behavior of electronic energy at fractional charges and fractional spins. In addition to improving results from conventional functionals for the prediction of ionization potentials, electron affinities, quasiparticle spectra, and reaction barrier heights, FSLOSC properly describes the dissociation of ionic species, single bonds, and multiple bonds without breaking space or spin symmetry and corrects the spurious fractional-charge dissociation of heteroatom molecules of conventional functionals. Thus, FSLOSC demonstrates success in reducing delocalization error and including strong correlation, within low-cost density functional approximation.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ., Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012575

OSTI ID:: 1469268

Alternate ID(s):: OSTI ID: 1540302

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 115 Journal Issue: 39; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 43 works

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