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) |
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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. |
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作者姓名: | 李福君 洒荣建 吴克琛 |
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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
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基金项目: | 国家自然科学基金,the MOST,Natural Science Foundation of Fujiaa Province |
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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.
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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 |
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