Exact Second-Order Corrections and Accurate Quasiparticle Energy Calculations in Density Functional Theory.

Journal Article (Journal Article)

We develop a second-order correction to commonly used density functional approximations (DFAs) to eliminate the systematic delocalization error. The method, based on the previously developed global scaling correction (GSC), is an exact quadratic correction to the DFA for the fractional charge behavior and uses the analytical second derivatives of the total energy with respect to fractional occupation numbers of the canonical molecular orbitals. For small and medium-size molecules, this correction leads to ground-state orbital energies that are a highly accurate approximation to the corresponding quasiparticle energies. It provides excellent predictions of ionization potentials, electron affinities, photoemission spectrum, and photoexcitation energies beyond previous approximate second-order approaches, thus showing potential for broad applications in computational spectroscopy.

Full Text

Duke Authors

Cited Authors

  • Mei, Y; Chen, Z; Yang, W

Published Date

  • August 2021

Published In

Volume / Issue

  • 12 / 30

Start / End Page

  • 7236 - 7244

PubMed ID

  • 34310157

Pubmed Central ID

  • PMC9367128

Electronic International Standard Serial Number (EISSN)

  • 1948-7185

International Standard Serial Number (ISSN)

  • 1948-7185

Digital Object Identifier (DOI)

  • 10.1021/acs.jpclett.1c01962

Language

  • eng