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

Journal Article · Tue Apr 21 04:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4918347· OSTI ID:22415664

Zhang, DaDi ^[1]; Zheng, Xiao ^[1]; Li, Chen ^[2]; Yang, Weitao ^[2]

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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)

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.

• OSTI ID: 22415664
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 15 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
ACCURACY
APPROXIMATIONS
CAPTURE
CORRECTIONS
DENSITY FUNCTIONAL METHOD
ELECTRONS
HARTREE-FOCK METHOD
RELAXATION
SELF-CONSISTENT FIELD