Calculation of the dynamic first electronic hyperpolarizability β(-ωσ; ω1, ω2) of periodic systems. Theory, validation, and application to multi-layer MoS2
Calculation of the dynamic first electronic hyperpolarizability β(-ωσ; ω1, ω2) of periodic systems. Theory, validation, and application to multi-layer MoS2
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DOI：
10.1063/1.4937770
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发表时间：
2015-12-28
影响因子：
4.4
通讯作者：
Dovesi, Roberto
中科院分区：
文献类型：
--
作者：
Maschio, Lorenzo;Rerat, Michel;Dovesi, Roberto
我们描述了基于2n + 1规则的完全解析方案的实现，用于计算耦合摄动Hartree Fock和Kohn-Sham动态第一超极化张量β (-omega(sigma))；周期1D（聚合物），2D（平板）和3D（晶体）体系的ω (1), ω (2)) [R]。Dovesi等人；量子化学，114,1287(2014)]，利用局部高斯型基集。将直流-波克尔斯张量（dc-P）和二次谐波生成张量（SHG）作为特例包括在内。验证了(1)满足对称性要求；（ii）以LiF为例，无限周期聚合物的结果与外推的有限低聚物计算一致，同样地，对于二维平板和三维晶体的构建；（iii）低频时，值收敛于静态情况；（iv）有关dc-P、SHG和一般过程的Bishop-deKee色散公式通过四次项再现。在多层二硫化钼上的初步SHG计算满意地再现了实验数据。(C) 2015 AIP出版有限责任公司
We describe our implementation of a fully analytical scheme, based on the 2n + 1 rule, for computing the coupled perturbed Hartree Fock and Kohn-Sham dynamic first hyperpolarizability tensor beta(-omega(sigma); omega(1), omega(2)) of periodic 1D (polymer), 2D (slab), and 3D (crystal) systems in the CRYSTAL code [R. Dovesi et al., Int. J. Quantum Chem. 114, 1287 (2014)], which utilizes local Gaussian type basis sets. The dc-Pockels (dc-P) and second harmonic generation (SHG) tensors are included as special cases. It is verified that (i) symmetry requirements are satisfied; (ii) using LiF as an example, the infinite periodic polymer result agrees with extrapolated finite oligomer calculations and, likewise, for the build-up to a 2D slab and a 3D crystal; (iii) the values converge to the static case for low frequencies; and (iv) the Bishop-deKee dispersion formulas relating dc-P, SHG, and general processes are reproduced through quartic terms. Preliminary SHG calculations on multi-layer MoS2 satisfactorily reproduce experimental data. (C) 2015 AIP Publishing LLC.