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Title: Orbital relaxation effects on Kohn–Sham frontier orbital energies in density functional theory

Abstract

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.

Authors:
 [1];  [1];  [2];  [2]
  1. Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026 (China)
  2. Department of Chemistry, Duke University, Durham, North Carolina 27708 (United States)
Publication Date:
OSTI Identifier:
22415664
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 15; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ACCURACY; APPROXIMATIONS; CAPTURE; CORRECTIONS; DENSITY FUNCTIONAL METHOD; ELECTRONS; HARTREE-FOCK METHOD; RELAXATION; SELF-CONSISTENT FIELD

Citation Formats

Zhang, DaDi, Zheng, Xiao, Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026, Li, Chen, Yang, Weitao, and Key Laboratory of Theoretical Chemistry of Environment, School of Chemistry and Environment, South China Normal University, Guangzhou 510006. Orbital relaxation effects on Kohn–Sham frontier orbital energies in density functional theory. United States: N. p., 2015. Web. doi:10.1063/1.4918347.
Zhang, DaDi, Zheng, Xiao, Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026, Li, Chen, Yang, Weitao, & Key Laboratory of Theoretical Chemistry of Environment, School of Chemistry and Environment, South China Normal University, Guangzhou 510006. Orbital relaxation effects on Kohn–Sham frontier orbital energies in density functional theory. United States. https://doi.org/10.1063/1.4918347
Zhang, DaDi, Zheng, Xiao, Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026, Li, Chen, Yang, Weitao, and Key Laboratory of Theoretical Chemistry of Environment, School of Chemistry and Environment, South China Normal University, Guangzhou 510006. 2015. "Orbital relaxation effects on Kohn–Sham frontier orbital energies in density functional theory". United States. https://doi.org/10.1063/1.4918347.
@article{osti_22415664,
title = {Orbital relaxation effects on Kohn–Sham frontier orbital energies in density functional theory},
author = {Zhang, DaDi and Zheng, Xiao and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 and Li, Chen and Yang, Weitao and Key Laboratory of Theoretical Chemistry of Environment, School of Chemistry and Environment, South China Normal University, Guangzhou 510006},
abstractNote = {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.},
doi = {10.1063/1.4918347},
url = {https://www.osti.gov/biblio/22415664}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 15,
volume = 142,
place = {United States},
year = {Tue Apr 21 00:00:00 EDT 2015},
month = {Tue Apr 21 00:00:00 EDT 2015}
}