用局域基组计算三维周期性化合物的静态电子二阶非线性极化率或三阶极化张量 chi(3)。

Calculation of the static electronic second hyperpolarizability or chi(3) tensor of three-dimensional periodic compounds with a local basis set.

机构信息

Dipartimento di Scienze e Tecnologie Avanzate, Universita del Piemonte Orientale, Viale T. Michel 11, 15121 Alessandria, Italy.

出版信息

J Chem Phys. 2009 Nov 14;131(18):184105. doi: 10.1063/1.3263919.

DOI:10.1063/1.3263919

PMID:19916596

Abstract

The coupled perturbed Hartree-Fock (CPHF) method for evaluating static first (beta) and second (gamma) hyperpolarizability tensors of periodic systems has recently been implemented in the CRYSTAL code [Bishop et al., J. Chem. Phys. 114, 7633 (2001)]. We develop here an efficient and accurate computational protocol, along with the local basis sets needed for first and second row atoms. Application is made to several high symmetry three-dimensional systems including one (pyrope) with an 80 atom unit cell. CPHF second-order hyperpolarizabilities substantially undershoot experimental values, due to an overestimate of the band gap, but trends are satisfactorily reproduced for beta as well as gamma.

摘要

最近，CRYSTAL 代码中已经实现了用于评估周期系统静态第一（β）和第二（γ）超极化率张量的耦合微扰哈特ree-fock（CPHF）方法[Bishop 等人，J. Chem. Phys. 114, 7633 (2001)]。我们在这里开发了一种高效准确的计算方案，以及用于第一和第二行原子的局部基集。应用于包括一个（pyrope）具有 80 个原子单元的几个高对称三维系统。CPHF 二阶超极化率由于带隙的高估而大大低于实验值，但β和γ的趋势都得到了令人满意的再现。