关键词: 电子转移, 电子转移矩阵元, 构型

Abstract: Based on the semi-classical theory of electron transfer,quantum chemical calculation at HF/6-31G level was performed for the study of intramolecular electron transfer between durene-bridged 2,5-dimethoxy-4-methylphenyl and its cation. Two configurations are adopted. After the geometric optimizations of the electron-localized states,a linear reaction coordinate ξ was introduced to determine the transition state. The electronic transfer matrix elementsV_ABare calculated by variation principle. The non-equilibrium solvation correction was taken into account. The electron transfer rate and reorganization energy obtained by theoretical calculation are consistent well with the experimental values. The electronic transfer matrix elements at different dihedral angles between bridge and redox centers were obtained. In order to show the different contribution to this value,the electronic transfer matrix elements were divided into two parts: through space and through bond. The latter is further divided into σ bond contribution and π bond one. It has been concluded that the through π bond coupling is proportional to the square of cosine of dihedral angle. This conclusion was explained qualitatively.

Key words: Electron transfer, Electron transfer matrix elements, Configuration