On the degeneracy of atomic states within exact-exchange (spin-) density functional theory

S. Pittalis; S. Kurth; E. K.U. Gross

doi:10.1063/1.2338038

On the degeneracy of atomic states within exact-exchange (spin-) density functional theory

S. Pittalis^*, S. Kurth, E. K.U. Gross

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

The problem of degenerate ground states of open-shell atoms is investigated in spin-restricted and spin-unrestricted density functional theories using the exact-exchange energy functional. For the spin-unrestricted case, spurious energy splittings of the order of 2-3 kcal/mol are found for atoms of the second and third periods which are larger than the splittings obtained from recently proposed approximate exchange functionals depending explicitly on the current density. In remarkable contrast, for spin-restricted calculations the degeneracy of different atomic ground states is recovered to within less than 0.6 kcal/mol.

Original language	English
Article number	084105
Journal	Journal of Chemical Physics
Volume	125
Issue number	8
DOIs	https://doi.org/10.1063/1.2338038
State	Published - 2006
Externally published	Yes

Bibliographical note

Funding Information:
We gratefully acknowledge financial support through the Deutsche Forschungsgemeinschaft Priority Program 1145 “First-Principles Methods,” through the EU Network of Excellence NANOQUANTA, and through the EU Research and Training Network EXCITING.

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title = "On the degeneracy of atomic states within exact-exchange (spin-) density functional theory",

abstract = "The problem of degenerate ground states of open-shell atoms is investigated in spin-restricted and spin-unrestricted density functional theories using the exact-exchange energy functional. For the spin-unrestricted case, spurious energy splittings of the order of 2-3 kcal/mol are found for atoms of the second and third periods which are larger than the splittings obtained from recently proposed approximate exchange functionals depending explicitly on the current density. In remarkable contrast, for spin-restricted calculations the degeneracy of different atomic ground states is recovered to within less than 0.6 kcal/mol.",

author = "S. Pittalis and S. Kurth and Gross, {E. K.U.}",

note = "Funding Information: We gratefully acknowledge financial support through the Deutsche Forschungsgemeinschaft Priority Program 1145 “First-Principles Methods,” through the EU Network of Excellence NANOQUANTA, and through the EU Research and Training Network EXCITING.",

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AU - Pittalis, S.

AU - Kurth, S.

AU - Gross, E. K.U.

N1 - Funding Information: We gratefully acknowledge financial support through the Deutsche Forschungsgemeinschaft Priority Program 1145 “First-Principles Methods,” through the EU Network of Excellence NANOQUANTA, and through the EU Research and Training Network EXCITING.

PY - 2006

Y1 - 2006

N2 - The problem of degenerate ground states of open-shell atoms is investigated in spin-restricted and spin-unrestricted density functional theories using the exact-exchange energy functional. For the spin-unrestricted case, spurious energy splittings of the order of 2-3 kcal/mol are found for atoms of the second and third periods which are larger than the splittings obtained from recently proposed approximate exchange functionals depending explicitly on the current density. In remarkable contrast, for spin-restricted calculations the degeneracy of different atomic ground states is recovered to within less than 0.6 kcal/mol.

AB - The problem of degenerate ground states of open-shell atoms is investigated in spin-restricted and spin-unrestricted density functional theories using the exact-exchange energy functional. For the spin-unrestricted case, spurious energy splittings of the order of 2-3 kcal/mol are found for atoms of the second and third periods which are larger than the splittings obtained from recently proposed approximate exchange functionals depending explicitly on the current density. In remarkable contrast, for spin-restricted calculations the degeneracy of different atomic ground states is recovered to within less than 0.6 kcal/mol.

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JO - Journal of Chemical Physics

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On the degeneracy of atomic states within exact-exchange (spin-) density functional theory

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