Giarrusso Sara, Gori-Giorgi Paola
Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, FEW, Vrije Universiteit, De Boelelaan 1083, Amsterdam, 1081HV, The Netherlands.
J Phys Chem A. 2020 Mar 26;124(12):2473-2482. doi: 10.1021/acs.jpca.9b10538. Epub 2020 Mar 16.
We analyze in depth two widely used definitions (from the theory of conditional probability amplitudes and from the adiabatic connection formalism) of the exchange-correlation energy density and of the response potential of Kohn-Sham density functional theory. We introduce a local form of the coupling-constant-dependent Hohenberg-Kohn functional, showing that the difference between the two definitions is due to a corresponding local first-order term in the coupling constant, which disappears globally (when integrated over all space), but not locally. We also design an analytic representation for the response potential in the strong-coupling limit of density functional theory for a model single stretched bond.
我们深入分析了科恩-沈密度泛函理论中交换关联能量密度和响应势的两种广泛使用的定义（来自条件概率振幅理论和绝热连接形式）。我们引入了耦合常数依赖的霍恩伯格-科恩泛函的局部形式，表明这两种定义之间的差异源于耦合常数中相应的局部一阶项，该项在全局（对所有空间积分时）消失，但在局部并不消失。我们还为模型单拉伸键在密度泛函理论的强耦合极限下的响应势设计了一种解析表示。
