联吡啶钌配合物中硫氰配位基团替代结构的设计与结构性质研究

项目名称： 联吡啶钌配合物中硫氰配位基团替代结构的设计与结构性质研究

项目编号： No.21201059

项目类型： 青年科学基金项目

立项/批准年度： 2013

项目学科： 无机化学

项目作者： 李明霞

作者单位： 黑龙江大学

项目金额： 25万元

中文摘要： 本项研究以提高染料的敏化性能及稳定性为目的，拟利用多齿环金属配体代替硫氰酸盐配体，设计系列新型环金属联吡啶钌配合物染料分子。利用密度泛函理论，优化染料分子基态和激发态的几何构型，计算激发态电子结构性质、激发态稳定性及激发态氧化还原势，计算染料分子的吸收光谱和发射光谱等光学性质。采用分子力学和量子力学相结合的方法，建立合理的理论模型，优化染料/TiO2的吸附几何构型，确定优先的吸附模式。研究染料在TiO2表面上的吸附、能级匹配及轨道相互作用。计算染料/TiO2吸附结构相关的电子结构性质、光学性质及发生在染料/TiO2界面上的电子传输性质。理论计算结合已有实验研究成果，深入分析染料分子结构与界面耦合作用、电子传输性质及敏化性能之间的内在关系，为设计和优化新型，高效的染料敏化剂，提高太阳能电池光电转化效率和稳定性提供可靠的理论依据和新的线索。

中文关键词： N-杂环卡宾吡啶；钌敏化剂；电子结构；吸收光谱；密度泛函

英文摘要： The purpose of this project is to enhance the efficiency and long-term stablity of the dye-sensitized solar cells(DSSC), to design the series novel thiocyanate-free cyclometalated ruthenium polypyridine complex, in which the thiocyanate ligands has been replace by the multidentate ligands. The density functional theory(DFT) and the time-dependent density funtional theory(TDDFT) are emploied to study the geometry structures of both the ground and the excited states,the electronic structures of the excited states,the excited state stability ,the excited state redox potential,the absportion and emission spectral properties of the dye sensitizers. The molecular mechanics and quantum mechanics methods are emploied to optimize the adsorption geometry structure and determinate the preferred adsorption mode of the dye on the TiO2 surface, to investigate the dynamics of dye adsorption,the energy levels matching and the interaction of the orbitals, and to study the electronic structure,optical properties of dye-TiO2 systems and the electronic transfer properties occurring at the dye/TiO2 interface. By combining the theoretical calculations with experimental results, the relation of the dye molecule structure and interfacial couple effect,the electronic transfer properties and sensitization performance are explored. The s

英文关键词： N-heterocyclic carbene-pyridine；ruthenium sensitizer；electronic structure；absorption spectrum；density functional theory