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