Weber Valéry, Niklasson Anders M N, Challacombe Matt
Department of Chemistry, University of Fribourg, 1700 Fribourg, Switzerland.
J Chem Phys. 2005 Jul 22;123(4):044106. doi: 10.1063/1.1944724.
Perturbed projection for linear scaling solution of the coupled-perturbed self-consistent-field equations [V. Weber, A.M.N. Niklasson, and M. Challacombe, Phys. Rev. Lett. 92, 193002 (2004)] is extended to the computation of higher-order static response properties. Although generally applicable, perturbed projection is further developed here in the context of the self-consistent first and second electric hyperpolarizabilities at the Hartree-Fock level of theory. Nonorthogonal, density-matrix analogs of Wigner's 2n+1 rule valid for linear one-electron perturbations are given up to fourth order. Linear scaling and locality of the higher-order response densities under perturbation by a global electric field are demonstrated for three-dimensional water clusters.
用于耦合微扰自洽场方程线性标度解的微扰投影法[V. 韦伯、A.M.N. 尼克拉斯森和M. 查拉科姆贝，《物理评论快报》92, 193002 (2004)]被扩展到高阶静态响应性质的计算。尽管微扰投影法一般适用，但在此是在哈特里 - 福克理论水平下自洽一阶和二阶超极化率的背景下进一步发展的。给出了适用于线性单电子微扰的维格纳2n + 1规则的非正交密度矩阵类似物，直至四阶。对于三维水团簇，证明了在全局电场微扰下高阶响应密度的线性标度和局域性。
