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arXiv physics/0605032physics.atom-ph
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精确交换(自旋)密度泛函理论中原子态的简并性

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

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

摘要:

在自旋受限和非受限密度泛函理论中,利用精确的交换能泛函,研究了开壳层原子的简并基态问题。对于自旋不受限制的情况下,寄生的能量分裂的顺序为2至3千卡/摩尔被发现的第二和第三周期的原子,这是大于分裂从最近提出的近似交换泛函明确取决于电流密度。与此相反,对于自旋限制计算,不同原子基态的简并度恢复到小于0.6千卡/摩尔。

英文摘要:

The problem of degenerate ground states of open-shell atoms is investigated in spin-restricted and unrestricted density functional theory using the exact exchange energy functional. For the spin-unrestricted case, spurious energy splittings of the order of 2 to 3 kcal/mol are found for atoms of the second and third period which is 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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