黄金规则用于 N－ 3＋ N3体系电子转移的研究

摘要

基于 B3P86/6 311＋ G优化的 N3与 N－ 3分子几何 ,确定了 N3＋ N－ 3基态电子转移体系的六种不同的耦合机理 ,及各种形式耦合络合物的几何性质、活化能、稳定化能、耦合矩阵元和态密度 ,并利用黄金规则计算了电子转移速率 ,讨论了各耦合方式对电子转移速率的影响 .%On the basis of the N3 and N－ 3molecular geometries optimized at the B3P86/6 311＋ G-level,six different coupling mechanism have been determined for the N3＋ N－ 3electron transfer system in the ground state,the corresponding geometrical properties,activation energy,stabilization energy,the coupling matrix elements and the density of the electronic state also have been predicted for the various coupling encounter complexes,the electron transfer rates have been calculated by using the Golden-rule scheme,the effect of the coupling pathways on the electron transfer rate has been discussed.