取代基对8-羟基喹啉金属配合物电子光谱和二阶非线性光学性质的影响

在B3LYP/LANL2DZ/6-31G^*水平上优化目标化合物分子的几何结构，并分别在TD- B3LYP/LANL2DZ/6-31++G^**和B3LYP/LANL2DZ/6-31++G^**水平计算目标化合物分子的电子吸收光谱和二阶非线性光学性质.计算结果表明，引入共轭给电子基使配合物分子的最大吸收波长红移，强共轭吸电子基的引入使配合物的最大吸收波长蓝移，取代基的引入使IrQ₃型配合物的二阶非线性光学性质明显增大.对AgQ型配合物，电子跃迁属于配体内部的电荷转移（LLCT）.对PtQ₂和IrQ₃型配合物，电子跃迁属于LLCT和部分金属向配体的电荷转移.取代基对AgQ，PtQ₂，IrQ₃型配合物分子的跃迁性质几乎无影响.关键词：8-羟基喹啉金属配合物电子光谱二阶非线性光学性质密度泛函理论

Effect of substituting groups on electronic spectra and second-order nonlinear optical properties of 8-hydroxyquinolinate metal complexes

Geometry optimization of target complexes were performed at the level of B3LYP/ LanL2DZ/6-31G^*, and their absorption spectra and the second nonlinear optical properties were calculated at the TD-B3LYP/LANL2DZ/6-31++G^** level and B3LYP/LANL2DZ/6-31++G^** level, respectively. The results indicate that the introduction of conjugated substituting groups of electron-donor and conjugated substituting groups of strong electron-accepter makes maximal absorption wavelength red-shifted and blue-shifted, respectively. The introduction of conjugated substituting groups resultes in obvious increase of second nonlinear optical properties for IrQ₃ complexes. The electronic transfer belongs to intra-ligand charge transfer （LLCT） for AgQ complexes, and LLCT mixed with partially metal-to-ligand charge transfer for PtQ₂ and IrQ₃ complexes. There is no effect of substituting groups on transition properties for AgQ, PtQ₂ and IrQ₃ complexes.