Orbital relaxation effects on Kohn-Sham frontier orbital energies in density functional theory.

Published

Journal Article

We explore effects of orbital relaxation on Kohn-Sham frontier orbital energies in density functional theory by using a nonempirical scaling correction approach developed in Zheng et al. [J. Chem. Phys. 138, 174105 (2013)]. Relaxation of Kohn-Sham orbitals upon addition/removal of a fractional number of electrons to/from a finite system is determined by a systematic perturbative treatment. The information of orbital relaxation is then used to improve the accuracy of predicted Kohn-Sham frontier orbital energies by Hartree-Fock, local density approximation, and generalized gradient approximation methods. The results clearly highlight the significance of capturing the orbital relaxation effects. Moreover, the proposed scaling correction approach provides a useful way of computing derivative gaps and Fukui quantities of N-electron finite systems (N is an integer), without the need to perform self-consistent-field calculations for (N ± 1)-electron systems.

Full Text

Duke Authors

Cited Authors

  • Zhang, D; Zheng, X; Li, C; Yang, W

Published Date

  • April 2015

Published In

Volume / Issue

  • 142 / 15

Start / End Page

  • 154113 -

PubMed ID

  • 25903872

Pubmed Central ID

  • 25903872

Electronic International Standard Serial Number (EISSN)

  • 1089-7690

International Standard Serial Number (ISSN)

  • 0021-9606

Digital Object Identifier (DOI)

  • 10.1063/1.4918347

Language

  • eng