四氰基乙烯-四甲基乙烯体系光诱导电子转移双势阱的从头算研 究

以两态模型为基础,用从头算方法,在DZP所有原子带极化函数的Dunning(9s,5p)/(3s,2p)]基组水平上对四氰基乙烯与四甲基乙烯间的电子转移进行理论计算。通过孤立给体和受体的几何构型优化,计算了给体的电离能和受体的电子亲和能。计算表明,在光诱导电荷分离之后的返回电子转移处于高放热的Marcus反转区。通过碰撞配合物的结构优化和电荷分离处理,在线性反应坐标近似下得到四甲基乙烯-四氰基乙烯配合物电荷分离反应的双势阱,进而获得反应热,键重组能,以及跃迁能。

Ab initio study of the photoinduced electron transfer between tetracyanoethylene and tetramethylethylene

Based on the two - state model, theoretical calculation has been performed for the photoinduced electron transfer (ET) between tetracyanoethylene (TCNE) and tetramethylethylene (TME) by use of the ab initio method at the level of DZP basis set Dunning's (9s,5p)/(3s,2p) basis sets with polarization functions on all atoms]. After geometric optimizations of the isolated donor and acceptor, the ionization potential of the donor and the electron affinity of the acceptor have been calculated. It has been found that the return ET after the photoinduced charge separation is in the highly exoenergic Marcus inverted region. Through the geometry optimization and the charge separation of the encounter complex, the double - well potential for the photoinduced charge separation reaction in the tetracyanoethylene - tetramethylethylene system has been constructed under the linear reaction coordinate. The reaction heat, the inner reorganization energy, and the transition energy, have been obtained.