| Theoretical Investigations of Nonlinear Optical Properties of Transition Metal Cluster Anions |
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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，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，Foundation of Fujian Province |
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| 摘 要： | In the framework of density functional theory （DFT）, the electronic excitations and nonlinear optical （NLO） properties of six binuclear transition metal cluster anions with the formula of Ch2M-（μ-Ch）2-M＇CN]^2- （M = Mo, W; Ch = S, Se; M＇ = Cu, Ag） have been systemically investigated at both cases of gas phase and DMF solution. The obtained electronic absorption spectra reveal that the element replacements of metals M and ligands Ch have significant influence on the absorptions, especially on the low-lying ones. In addition, the transitions of μ-Ch→M are dominant for the low-lying excitations, whereas the transitions of M＇→M as well as Ch→M are mainly responsible for the higher excitations. The calculated molecular first and second hyperpolarizabilities present the remarkable element substitution and solvent effects. The analyses show that the transitions involving μ-Ch→M charge transfer make the critical contributions to the first hyperpolarizability t, and that the charge transfers from the moieties of MCh4 to M＇CN as well as those of μ-Ch→M and M＇→M are responsible for the second hyperpolarizability y. Moreover, the introduction of solvent leads to the results that the transitions within the moieties of MCh4 and M＇CN make larger contributions to the hyperpolarizability, especially to γ.
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| 关 键 词： | 金属簇阴离子 密度泛函理论 元素取代效应 溶剂效应 |
Theoretical Investigations of Nonlinear Optical Properties of Transition Metal Cluster Anions |
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| Authors: | LIU Cai-Ping SA Rong-Jian MANG Chao-Yong LI Qiao-Hong LI Fu-Jun WU Ke-Chen |
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| Institution: | 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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| Abstract: | In the framework of density functional theory (DFT), the electronic excitations and nonlinear optical (NLO) properties of six binuelear transition metal cluster anions with the formula of Ch2M-(μ-Ch)2-M'CN]2-(M = Mo, W; Ch = S, Se; M' = Cu, Ag) have been systemically investigated at both cases of gas phase and DMF solution. The obtained electronic absorption spectra reveal that the element replacements of metals M and ligands Ch have significant influence on the absorptions, especially on the low-lying ones. In addition, the transitions of μ-Ch→M are dominant for the low-lying excitations, whereas the transitions of M'→M as well as Ch→M are mainly responsible for the higher excitations. The calculated molecular first and second hyper- polarizabilities present the remarkable element substitution and solvent effects. The analyses show that the transitions involving μ-Ch→M charge transfer make the critical contributions to the first hyperpolarizability β, and that the charge transfers from the moieties of MCh4 to M'CN as well as those of β-Ch→M and M'→M are responsible for the second hyperpolarizability γ. Moreover, the introduction of solvent leads to the results that the transitions within the moieties of MCh4 and M'CN make larger contributions to the hyperpolafizability, especially to γ. |
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| Keywords: | transition metal cluster anions density functional theory electronic excitation spectra hyperpolarizability element substituting effect solvent effect |
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