1. Orbital relaxation effects on Kohn-Sham frontier orbital energies in density functional theory.
- Author
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DaDi Zhang, Xiao Zheng, Chen Li, and Weitao Yang
- Subjects
- *
DENSITY functional theory , *FRONTIER orbitals , *ELECTRONS , *APPROXIMATION theory , *RELAXATION (Gas dynamics) - 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. [ABSTRACT FROM AUTHOR]
- Published
- 2015
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