关键词: 乙烯P, 电子转移, 光诱导, 从头计算法, 几何异构

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.

Key words: ETHYLENE P, PHOTOINDUCED, AB INITIO CALCULATION, GEOMETRICAL ISOMERISM