金属—苯重组能的计算

The calculation of inner-sphere reorganization for metal benzene complex

基于捕获力场潜能的模型和Bates提出的绝热不变性理论 ,采用改进了的平均偶极矩理论 (IADO理论 ) ,我们计算了过渡金属离子—苯配合物之间的力常数及一系列内氛重组能 ,讨论了理论计算结果与实验结果之间差别的原因 .结果表明该工作有效地改进了前人的工作 ,取得了与实验光谱标度数据一致的规律性 ,并与光发射实验结果吻合较好 ,它避免了因缺乏溶液中可信的振动光谱数据在内氛重组能计算上的困难 ,通过易得的离子和配体的物理量给出了一种简便的分析方法 .

From the view of structure of coordination ions,the effect of the structural reorganization energy(RE) of reactions in electron transfer rate may be divided into two parts:inner sphere factor(RE in )and outer sphere factor (RE out ). The RE out may be accurately calculated via the Marcus of non equilibrium solvent polarization,but there are also some errors in them.Based on a simple improved model of reorganization phenomenon and ion dipole capture force field potential, a new formalism of energy index describing the inner sphere reorganization effect of hydrated ions in solution involved in electron transfer processes in presented in this paper,the calculation results indicate that this work effectively improve early ones,and give a better agreement with experimental spectroscopic scale date and photoemission experimental results,and present a new simple analysis method by the physical parameters of ions and ligands with is obtained easily.