论文标题

分数电荷的密度功能理论:局部,尺寸一致性和交换相关性

Density functional theory for fractional charge: Locality, size consistency, and exchange-correlation

论文作者

Kong, Jing

论文摘要

当整数电荷的确切通用功能将其应用于由渐近分离密度制成的系统时,将其渐近地扩展到分数电荷。扩展功能在渐近局部,据说是I-Local。将函数应用于在两个渐近分离的区域中分布的核的系统,需要在每个语言环境中明确搜索电子电荷。搜索的结果导致分子大小一致性原理。在物理上,将分子的概念扩展到包括分数的电子(称为分子分子)作为可局部可观察的可观察的概念,其电子能将其定义为分数电荷的通用功能的legendre变换。存在分子分子的密度和外部电势之间的一对一映射。该功能相对于电子数量的众所周知的分段线性性仅适用于渐近分离的V-代表性密度。另一方面,对于近似I局部通用函数,对于整数电子数量而言,这种情况是必需的。分子分子的KS动力学函数的定义很好,并且具有与整数电荷系统相同的形式。证明是I-Local。非排效机集合V-代表性的分数密度同时与KS非互动假设表示不相互作用的波函数。对一组代表波函数的一组搜索产生了与分数占用有关的交换相关功能。它被证明是分数分子的正式KS交换与相关能量的上限,并包括强相关性。新功能为有效的文献中有效分数占用的示例提供了正确的结果。

The exact universal functional of integer charge leads to an extension to fractional charge asymptotically when it is applied to a system made of asymptotically separated densities. The extended functional is asymptotically local and is said to be i-local. Applying the functional to a system with nuclei distributed in two asymptotically separated locales requires an explicit search of the electronic charge at each locale. The result of the search leads to the molecular size consistency principle. It is physically sensible to extend the concept of molecule to include fractional number of electrons (called fractional molecule) as a localizable observable, with its electronic energy defined as a Legendre transform of the universal functional of fractional charge. A one-to-one mapping between the density and the external potential of a fractional molecule exists. The well-known piecewise linearity of the functional with respect to the number of electrons is shown to hold only for asymptotically isolated v-representable densities. On the other hand, this condition is necessary for an approximate i local universal functional to be accurate for integer number of electrons. The KS kinetic functional for a fractional molecule is well defined and has the same form as that for a system of integer charge. It is shown to be i-local. A nondegenerate ensemble v-representable fractional density is simultaneously noninteracting wavefunction representable with the KS noninteracting assumption. A constrained search over a set of those representing wavefunctions yields an exchange-correlation functional pertaining to fractional occupancies. It is shown to be an upper-bound to the formal KS exchange-correlation energy of the fractional molecule and includes strong correlation. The new functional yields the correct result for a well-designed example of effective fractional occupancies in literature.

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