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TDDFT Study on the Electronic Excitations and First Hyperpolarizabilities of Mixed-metal Carbonyl Clusters W2Ir2(μ-L)(CO)8(η^5-C5H4Me)2(L = dppe/dppf)
引用本文:李福君,洒荣建,吴克琛. TDDFT Study on the Electronic Excitations and First Hyperpolarizabilities of Mixed-metal Carbonyl Clusters W2Ir2(μ-L)(CO)8(η^5-C5H4Me)2(L = dppe/dppf)[J]. 结构化学, 2009, 28(1): 99-105
作者姓名:李福君  洒荣建  吴克琛
作者单位:State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,The Chinese Academy of Sciences,Fuzhou,Fujian 350002,China  
基金项目:国家自然科学基金,the MOST,Natural Science Foundation of Fujiaa Province 
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.

关 键 词:TDDFT  紫外光谱  过渡金属  非线性光谱  混合金属碳酰基簇

TDDFT Study on the Electronic Excitations and First Hyperpolarizabilities of Mixed-metal Carbonyl Clusters W2Ir2(μ-L)(CO)8(η5-C5H4Me)2(L=dppe/dppf)
LI Fu-Jun,SA Rong-Jian,WU Ke-Chen. TDDFT Study on the Electronic Excitations and First Hyperpolarizabilities of Mixed-metal Carbonyl Clusters W2Ir2(μ-L)(CO)8(η5-C5H4Me)2(L=dppe/dppf)[J]. Chinese Journal of Structural Chemistry, 2009, 28(1): 99-105
Authors:LI Fu-Jun  SA Rong-Jian  WU Ke-Chen
Affiliation:State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,The Chinese Academy of Sciences,Fuzhou,Fujian 350002,China
Abstract:Mixed-metal carbonyl clusters of W2Ir2(CO)10(η5-C5H4Me)2 1 and W2Ir2(μ-L)(CO)8(η5-C5H4Me)2(L=dppe 2,dppf 3)have been studied by TDDFT method focusing on their electronicand nonlinear optical properties.These three clusters exhibit the first static hyperpolarizabilities ofmedium magnitude (βtot~10×10-30 esu).The origin of βis discussed by the new proposed orbital-pairdecomposition scheme by Barandes et al.The result suggests that the β values of the two clusters aremainly originated from d-d electron transition within the metal skeleton,and d-p(π*)electrontransition from metals to carbonyls and phenyl.The additional coordination by the electron donorgroup,ferrocene,makes cluster 3 own much largerβvalues,and the relatively longer range chargetransfer from d orbitals of ferrocene to d orhirals of Ir and W is responsible for the enhanced βvalues.
Keywords:TDDFT  UV-vis spectrum  transition metal  nonlinear optical
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