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

Publication ,  Journal Article
Zhang, D; Zheng, X; Li, C; Yang, W
Published in: The Journal of chemical physics
April 2015

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.

Duke Scholars

Published In

The Journal of chemical physics

DOI

EISSN

1089-7690

ISSN

0021-9606

Publication Date

April 2015

Volume

142

Issue

15

Start / End Page

154113

Related Subject Headings

  • Chemical Physics
  • 51 Physical sciences
  • 40 Engineering
  • 34 Chemical sciences
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences
 

Citation

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Zhang, D., Zheng, X., Li, C., & Yang, W. (2015). Orbital relaxation effects on Kohn-Sham frontier orbital energies in density functional theory. The Journal of Chemical Physics, 142(15), 154113. https://doi.org/10.1063/1.4918347
Zhang, DaDi, Xiao Zheng, Chen Li, and Weitao Yang. “Orbital relaxation effects on Kohn-Sham frontier orbital energies in density functional theory.The Journal of Chemical Physics 142, no. 15 (April 2015): 154113. https://doi.org/10.1063/1.4918347.
Zhang D, Zheng X, Li C, Yang W. Orbital relaxation effects on Kohn-Sham frontier orbital energies in density functional theory. The Journal of chemical physics. 2015 Apr;142(15):154113.
Zhang, DaDi, et al. “Orbital relaxation effects on Kohn-Sham frontier orbital energies in density functional theory.The Journal of Chemical Physics, vol. 142, no. 15, Apr. 2015, p. 154113. Epmc, doi:10.1063/1.4918347.
Zhang D, Zheng X, Li C, Yang W. Orbital relaxation effects on Kohn-Sham frontier orbital energies in density functional theory. The Journal of chemical physics. 2015 Apr;142(15):154113.

Published In

The Journal of chemical physics

DOI

EISSN

1089-7690

ISSN

0021-9606

Publication Date

April 2015

Volume

142

Issue

15

Start / End Page

154113

Related Subject Headings

  • Chemical Physics
  • 51 Physical sciences
  • 40 Engineering
  • 34 Chemical sciences
  • 09 Engineering
  • 03 Chemical Sciences
  • 02 Physical Sciences