TDDFT Study on the Electronic Excitations and First Hyperpolarizabilities of Mixed-metal Carbonyl Clusters W_2Ir_2(μ-L)(CO)_8(η～5-C_5H_4Me)_2(L=dppe/dppf)

作     者：李福君 洒荣建 吴克琛 

作者机构：State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter The Chinese Academy of Sciences 

出 版 物：《Chinese Journal of Structural Chemistry》 (结构化学（英文）)

年 卷 期：2009年第28卷第1期

页      面：99-105页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：Supported by the National Natural Science Foundation of China (20573114) the MOST (2006DFA43020) Natural Science Foundation of Fujian Province (2006F3133) 

主　　题：TDDFT UV-vis spectrum transition metal nonlinear optical 

摘      要：Mixed-metal carbonyl clusters of W2Ir2（CO）10（η^5-C5H4Me）2 1 and W2Ir2（μ-L）（CO）8（η^5-C5H4Me）2 （L = dppe 2, dppf 3） have been studied by TDDFT method focusing on their electronic and nonlinear optical properties. These three clusters exhibit the first static hyperpolarizabilities of medium magnitude （βtot-10×10^-30 esu）. The origin of β is discussed by the new proposed orbital-pair decomposition scheme by Barandes et al. The result suggests that the β values of the two clusters are mainly originated from d-d electron transition within the metal skeleton, and d-p （π＊） electron transition from metals to carbonyls and phenyl. The additional coordination by the electron donor group, ferrocene, makes cluster 3 own much larger β values, and the relatively longer range charge transfer from d orbitals of ferrocene to d orbirals of Ir and W is responsible for the enhanced β values.