吩噻嗪与四甲基哌啶氧铵正离子的电子转移反应动力学研究

Dynamic Study of the Electron Transfer Reaction of Phenothiazine with 2,2,6,6-Tetramethyl-4-oxypiperidinyl-1-oxy cation

以Marcus半经典电子转移理论为基本框架, 改进了重组能的计算方法, 建立了一套研究自交换和交叉电子转移反应的理论方案。用密度泛函理论和半经验分子轨道理论具体研究了四甲基哌啶氧铵正离子与吩噻嗪在乙腈溶液中的交叉电子转移反应以及相应的2个自交换反应的动力学性质, 计算了反应的活化能、重组能、耦合矩阵元等有关参数,获得了和实验结果相一致的电子转移速率常数。

To study self-exchange and cross electron transfer reactions in solution, a theoretical scheme which can improve the calculation methods of inner- and outer-sphere reorganization energies was presented based on the semiclassical treatment of electron transfer reactions. The scheme was also applied to the cross electron transfer reaction of phenothiazine with 2, 2, 6, 6-tetramethyl-4-methoxypiperidinyl-1-oxy cation, and to the two self-exchange reactions related with the cross reaction. The activation energies, reorganization energies, coupling matrix elements and theoretical rate constants of the three reactions were obtained. The theoretical results are in good agreement with the experimental findings.