On the degeneracy of atomic states within exact-exchange (spin-) density functional theory.
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.
Pittalis
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Institut für Theoretische Physik, Freie Universität Berlin, Arnimallee 14, D-14195 Berlin, Germany.
Kurth
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Gross
E K U
EK