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

Published

Journal Article

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.

Full Text

Duke Authors

Cited Authors

  • Su, NQ; Li, C; Yang, W

Published Date

  • September 10, 2018

Published In

Volume / Issue

  • 115 / 39

Start / End Page

  • 9678 - 9683

PubMed ID

  • 30201706

Pubmed Central ID

  • 30201706

Electronic International Standard Serial Number (EISSN)

  • 1091-6490

International Standard Serial Number (ISSN)

  • 0027-8424

Digital Object Identifier (DOI)

  • 10.1073/pnas.1807095115

Language

  • eng