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 

机构地区：[1]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences

出　　处：《Chinese Journal of Structural Chemistry》2009年第1期99-105,共7页结构化学（英文）

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

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.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.

关 键 词：TDDFT UV-vis spectrum transition metal nonlinear optical 

分 类 号：O641[理学—物理化学]