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精确积分约束仅要求基态电子密度作为球形原子交换关联力 - ∂(V)(xc)(r)/∂(r) 的输入。

Exact integral constraint requiring only the ground-state electron density as input on the exchange-correlation force - partial differential(V)(xc)(r)/partial differential(r) for spherical atoms.

作者信息

March N H, Nagy A

机构信息

Department of Physics, University of Antwerp, Antwerp, Belgium and Oxford University, Oxford, England.

出版信息

J Chem Phys. 2008 Nov 21;129(19):194114. doi: 10.1063/1.3013808.

Abstract

Following some studies of integral(n)(r)inverted DeltaV(r)dr by earlier workers for the density functional theory (DFT) one-body potential V(r) generating the exact ground-state density, we consider here the special case of spherical atoms. The starting point is the differential virial theorem, which is used, as well as the Hiller-Sucher-Feinberg [Phys. Rev. A 18, 2399 (1978)] identity to show that the scalar quantity paralleling the above vector integral, namely, integral(n)(r) partial differential(V)(r)/partial differential(r)dr, is determined solely by the electron density n(0) at the nucleus for the s-like atoms He and Be. The force - partial differential(V)/ partial differential(r) is then related to the derivative of the exchange-correlation potential V(xc)(r) by terms involving only the external potential in addition to n(r). The resulting integral constraint should allow some test of the quality of currently used forms of V(xc)(r). The article concludes with results from the differential virial theorem and the Hiller-Sucher-Feinberg identity for the exact many-electron theory of spherical atoms, as well as for the DFT for atoms such as Ne with a closed p shell.

摘要

在早期工作者对积分(\int_{n}(r)\Delta V(r)dr)进行了一些关于密度泛函理论(DFT)的单粒子势(V(r))(该势产生精确的基态密度)的研究之后,我们在此考虑球形原子的特殊情况。出发点是微分维里定理,该定理以及希勒 - 苏彻 - 费恩伯格[《物理评论A》18, 2399 (1978)]恒等式被用于表明,与上述矢量积分平行的标量量,即(\int_{n}(r)\frac{\partial V(r)}{\partial r}dr),对于类(s)原子(He)和(Be),仅由原子核处的电子密度(n(0))决定。然后,力(-\frac{\partial V}{\partial r})通过除(n(r))之外仅涉及外部势的项与交换关联势(V_{xc}(r))的导数相关。由此产生的积分约束应该能够对当前使用的(V_{xc}(r))形式的质量进行一些检验。文章最后给出了球形原子精确多电子理论以及具有封闭(p)壳层的原子(如(Ne))的DFT的微分维里定理和希勒 - 苏彻 - 费恩伯格恒等式的结果。

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