First-principle study on polarizability and hyperpolarizability of a transition metal cluster, [Mo₂S₃(C₆H₁₁)₃(CO)₆]·N(C₂H₃)₄

Issue title: Computational aspects of electric polarizability calculations: Atoms, Molecules and clusters, Part I

Article type: Research Article

Authors: Wu, Kechen^{; *} | Liu, Ping | Zhou, Zhangfeng | Lin, Chensheng | Zhuang, Botao

Affiliations: State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China

Correspondence: [*] Corresponding author. Fax: +86 591 3714946; E-mail: wkc@ms.fjirsm.ac.cn.

Abstract: We reported the first-principle study of linear and nonlinear optical polarizability of a di-nuclear transition metal cluster, [Mo2S3(CO)6(C6H11)3]·N(C2H3)4, by using finite-field method. The calculations were performed at an HF/Lanl2dz level. The spatial average value of the first hyperpolarizability along z direction was very large, βz=13.8×10−30 esu, indicating the potential applications of this cluster for IR nonlinear optical processes. Our results showed that the charge transfer inside the metal core cluster, [Mo2S3(CO)6], played an important role in nonlinear optical response while the joint effect of metal core and organic ligands (C6H11)3 also contributed to nonlinear optical polarizability. In addition, the organic ionic group, [N(C2H3)4]+, situated in z direction enhanced the βz value. The study may help us to understand the nonlinear optical nature of the transition metal clusters and provided an example to show the computational efficiency of finite-field method in the first-principle theoretical study of the complex system containing transition-metal element.

Keywords: hyperpolarizability, finite-field method, transition metal cluster

DOI: 10.3233/JCM-2004-4320

Journal: Journal of Computational Methods in Sciences and Engineering, vol. 4, no. 3, pp. 451-459, 2004