skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Energies of isoelectronic atomic ions from a successful metageneralized gradient approximation and other density functionals

Abstract

We show that the poor performance of approximate Kohn-Sham (KS) density functional theory for highly charged atomic ions is improved dramatically by ensuring that (i) the exchange functional recovers the correct leading term in the Z expansion of the exchange energy (Z is the nuclear charge) and (ii) the correlation functional is bounded under uniform scaling of the density to the high-density limit--i.e., lim{sub {lambda}}{sub {yields}}{sub {infinity}}E{sub c}{sup KS}[n{sub {lambda}}]>-{infinity}, where n{sub {lambda}}(r)={lambda}{sup 3}n({lambda}r). The performance of several density functionals (BLYP, BP86, VS98, HCTH/407, PBE, PKZB, and TPSS) is compared for the 4-, 10-, and 18-electron atomic series spanning values of Z from 4 to 28. Especially accurate results are obtained with the nonempirical metageneralized gradient approximation of Tao, Perdew, Staroverov, and Scuseria (TPSS). High-Z limits of selected exchange and correlation functionals are evaluated and compared with the exact values.

Authors:
; ; ; ;  [1]
  1. Department of Chemistry, Rice University, Houston, Texas 77005 (United States)
Publication Date:
OSTI Identifier:
20643894
Resource Type:
Journal Article
Journal Name:
Physical Review. A
Additional Journal Information:
Journal Volume: 70; Journal Issue: 1; Other Information: DOI: 10.1103/PhysRevA.70.012502; (c) 2004 The American Physical Society; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 1050-2947
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; ATOMIC IONS; ATOMIC NUMBER; CATIONS; DENSITY FUNCTIONAL METHOD; ELECTRON CORRELATION; ELECTRONS; EXCHANGE INTERACTIONS; GROUND STATES; PERFORMANCE

Citation Formats

Staroverov, Viktor N, Scuseria, Gustavo E, Perdew, John P, Jianmin, Tao, Davidson, Ernest R, Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118, and Department of Chemistry, University of Washington, Seattle, Washington 98195. Energies of isoelectronic atomic ions from a successful metageneralized gradient approximation and other density functionals. United States: N. p., 2004. Web. doi:10.1103/PhysRevA.70.012502.
Staroverov, Viktor N, Scuseria, Gustavo E, Perdew, John P, Jianmin, Tao, Davidson, Ernest R, Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118, & Department of Chemistry, University of Washington, Seattle, Washington 98195. Energies of isoelectronic atomic ions from a successful metageneralized gradient approximation and other density functionals. United States. doi:10.1103/PhysRevA.70.012502.
Staroverov, Viktor N, Scuseria, Gustavo E, Perdew, John P, Jianmin, Tao, Davidson, Ernest R, Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118, and Department of Chemistry, University of Washington, Seattle, Washington 98195. Thu . "Energies of isoelectronic atomic ions from a successful metageneralized gradient approximation and other density functionals". United States. doi:10.1103/PhysRevA.70.012502.
@article{osti_20643894,
title = {Energies of isoelectronic atomic ions from a successful metageneralized gradient approximation and other density functionals},
author = {Staroverov, Viktor N and Scuseria, Gustavo E and Perdew, John P and Jianmin, Tao and Davidson, Ernest R and Department of Physics and Quantum Theory Group, Tulane University, New Orleans, Louisiana 70118 and Department of Chemistry, University of Washington, Seattle, Washington 98195},
abstractNote = {We show that the poor performance of approximate Kohn-Sham (KS) density functional theory for highly charged atomic ions is improved dramatically by ensuring that (i) the exchange functional recovers the correct leading term in the Z expansion of the exchange energy (Z is the nuclear charge) and (ii) the correlation functional is bounded under uniform scaling of the density to the high-density limit--i.e., lim{sub {lambda}}{sub {yields}}{sub {infinity}}E{sub c}{sup KS}[n{sub {lambda}}]>-{infinity}, where n{sub {lambda}}(r)={lambda}{sup 3}n({lambda}r). The performance of several density functionals (BLYP, BP86, VS98, HCTH/407, PBE, PKZB, and TPSS) is compared for the 4-, 10-, and 18-electron atomic series spanning values of Z from 4 to 28. Especially accurate results are obtained with the nonempirical metageneralized gradient approximation of Tao, Perdew, Staroverov, and Scuseria (TPSS). High-Z limits of selected exchange and correlation functionals are evaluated and compared with the exact values.},
doi = {10.1103/PhysRevA.70.012502},
journal = {Physical Review. A},
issn = {1050-2947},
number = 1,
volume = 70,
place = {United States},
year = {2004},
month = {7}
}