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

Abstract

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.

Authors:
ORCiD logo [1];  [1];  [2]
+ Show Author Affiliations
  1. Department of Chemistry, Duke University, Durham, NC 27708,
  2. 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
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Complex Materials from First Principles (CCM); Temple Univ., Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1469268
Alternate Identifier(s):
OSTI ID: 1540302
Grant/Contract Number:  
SC0012575
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 39; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Su, Neil Qiang, Li, Chen, and Yang, Weitao. Describing strong correlation with fractional-spin correction in density functional theory. United States: N. p., 2018. Web. doi:10.1073/pnas.1807095115.
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Su, Neil Qiang, Li, Chen, & Yang, Weitao. Describing strong correlation with fractional-spin correction in density functional theory. United States. https://doi.org/10.1073/pnas.1807095115
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Su, Neil Qiang, Li, Chen, and Yang, Weitao. Mon . "Describing strong correlation with fractional-spin correction in density functional theory". United States. https://doi.org/10.1073/pnas.1807095115.
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@article{osti_1469268,
title = {Describing strong correlation with fractional-spin correction in density functional theory},
author = {Su, Neil Qiang and Li, Chen and Yang, Weitao},
abstractNote = {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.},
doi = {10.1073/pnas.1807095115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 39,
volume = 115,
place = {United States},
year = {Mon Sep 10 00:00:00 EDT 2018},
month = {Mon Sep 10 00:00:00 EDT 2018}
}
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https://doi.org/10.1073/pnas.1807095115
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