溶剂-导体界面电子转移溶剂重组能的球-界面模型

在连续介质理论基础上, 根据热力学基本原理, 用一个外加电场Eex将非平衡态2Enon2, Dnon2]变成约束平衡态E*2, D*2], 推导出了正确普适的溶剂重组能公式. 基于球-界面近似, 推导出了正确的溶剂-导体界面电子转移溶剂重组能公式. 和Marcus的公式相比, 本文的结果多了(εs-εop)/(εop(εs-1))因子. 对极性溶剂, 预测的溶剂重组能约为Marcus模型所得结果的一半. 以C343(Coumarin 343)-TiO2体系为算例, 计算了溶剂重组能并与实验值进行了比较.

A Sphere-Interface Model for the Solvent Reorganization Energy in an Electron Transfer Reaction at the Solvent/Conductor Interface

Based on the continuum medium theory and the basic principles of thermodynamics we used an extra electric field Eex to change the non-equilibrium salvation state 2Enon2, Dnon2] to a constrained equilibrium state E*2, D*2]. A novel expression of solvent reorganization energy was deduced. Furthermore, by adopting the sphere-interface approximation we deduced the formula for the solvent reorganization energy of the electron transfer reaction occurring at the interface of the conductor and the solvent. Compared to the traditional Marcus model our result was scaled by a factor of (εs-εop)/(εop(εs-1)) which is about 0.5 in a polar solvent. C343(Coumarin 343)-TiO2 was used as an example and the analytical results using our model were discussed with respect to experimental measurements.