N，N-二甲基苯胺和苯醌间光诱导电荷转移

研究了N ,N 二甲基苯胺和苯醌间光诱导电荷转移的溶剂效应 .首先在B3LYP/ 6 31G 水平上对给体和受体进行构型优化 ,然后采用优化的给受体构型在Cs 对称性下计算得到两种相对稳定的复合物构象P和T .在CIS/ 6 31+G 水平上计算复合物气相激发态 ,结果发现 ,构象P的第三单重激发态发生分子间的完全电荷分离 ,构象T的第三激发单重态发生分子间的部分电荷分离 .在上述同样水平上计算复合物溶剂条件下的激发态性质 ,与气相结果相比表明 ,溶剂中两种构象的第三单重激发态均发生完全电荷分离 ,吸收光谱均发生较大红移 .

Photoinduced Charge Transfer between N,N-dimethylaniline and Quinone

The solvent effect on the photoinduced charge transfer between N,N-dimethylaniline and quinone has been investigated. Geometries of the isolated donor and acceptor have been optimized using B3LYP/6-31G ** method. Two relative stable conformers P and T of the complex have been obtained with the symmetry of C s. Excited states of the complex have been calculated at the level of CIS/6-31+G ** in the gas phase. The results indicate that the complete charge separation within the complex occurs in the third excited singlet state of P, but only partial charge transfer for the same excited state of T. At the same basis level, excited states of the complex in the solution have been investigated. Comparing the results in the solution with the gas-phase ones, the charge separation of the third excited singlet states of both conformers is found fairly well. The absorption spectrum in the solution has a large red shift.