C60-多吡啶Ru(II)配合物电子光谱的密度泛函理论研究

应用密度泛函理论(DFT)方法对两种C60-多吡啶Ru(II)衍生物进行理论研究. 在TZP全电子基组优化构型基础上, 通过分析前线轨道组成, 探讨金属及配体对C60母体影响; 以LB及SAOP校正局域密度近似, 用含时密度泛函(TDDFT)方法, 考虑溶剂化效应, 计算化合物1和2的电子吸收光谱. 结果表明, 化合物1和2在气相与丙酮溶液中所对应的光谱值差异较为明显, 溶剂化效应使吸收光谱蓝移. 计算得到化合物1和2在丙酮溶液中电子光谱与实验值吻合较好, 低能跃迁多为金属参与的混合跃迁, 高能跃迁主要由C60与配体部分贡献.

Theoretical Investigation on Electronic Spectra of Fullerene Polypyridyl Ruthenium(II) Complexes by Density Functional Theory

Theoretical investigation on two derivatives of Ru(bpy)n-C60]2 (bpy: 2,2-bipyridine; n=2, 3) has been performed by density functional theory. At TZP level, the compositions of frontier orbitals have been calculated in order to discuss the influence on C60 by metal and ligands. Taking into account solvent effects, the absorption spectra were investigated by time-dependent density functional theory (TDDFT) with LB94 and SAOP functional to correct local density approximation. The results show that inclusion of the solvent leads to important change of absorption spectra, and solvation induces a blue shift to some extent. The spectra calculated in the presence of the solvent are in good agreement with the experiment. Low energy transitions were found to originate mainly from the mixed transitions containing the metal, whereas the higher energy band arises from C60 and ligand charge transfer transitions.