溶液中离子－偶极子俘获力常数及离子内氛重组能标度

THE ION DIPOLE CAPTURE FORCE CONSTANTS AND THE SCALE OF INNER-SPHERE REORGANIZATION ENERGYOF TRANSITION METAL COORDINATION CATIONS IN SOLUTION

本文基于重组现象改进的自交换模型及离子－偶极子俘获力场势，提出了描述外氛电子转移机理中溶液离子内氛重组织效应的能量指标的一种新的标度方法，并对公式中所含参数利用离子－偶极子俘获力场势进行了确定。结果表明该方法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结论，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计算内氛重组能上的困难，通过易得的离子和配体的性质参数给出了一种简便而精确的计算方案。

Based on improved self-exchange model of reorganization phenomenon and ion-dipole capture force field potential,a new formalism of energy index describing the innersphere reorganiza tion effect of hydrated ions in solution involved in electron-transfer processes is presented. The calculation results indicate that this work effectrively improves previous ones,and gives better agreement with experimental spectroscopic scale data and photoemission experimental results,and avoidsthe difficulty to calculate inner-sphere RE under the condition of the scarcity of vibrational spectroscopic data in solution. Thus presents a new simple analytical method by the physical parameters ofions and ligands which is obtained readily.