Dipartimento di Scienze e Tecnologie Avanzate, Universita del Piemonte Orientale, Viale T. Michel 11, 15121 Alessandria, Italy.
J Chem Phys. 2009 Nov 14;131(18):184105. doi: 10.1063/1.3263919.
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.
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。
