溶液中电子自交换反应偶合矩阵元的直接计算  

DIRECT DETERMINATION OF ELECTRON TRANSFER INTEGRAL FOR SELF-EXCHANGE REACTIONS IN SOLUTION

作　　者：李淑范[1] 步宇翔[2] 

机构地区：[1]东北电力学院信息化教学中心,吉林省吉林市132012 [2]曲阜师范大学化学系,山东省曲阜市273165

出　　处：《曲阜师范大学学报（自然科学版）》2000年第3期65-68,共4页Journal of Qufu Normal University(Natural Science)

基　　金：国家自然科学基金!(29730 22);山东省自然科学基金 !(Y98B043)

摘　　要：基于实验电子转移速率数据 ,提出了一种实验确定溶液中水合离子对间电子自交换反应偶合矩阵元的新理论方案 .利用改进的自交换活化模型和从abinitio计算的单组分数据点拟合的精确位能面对所含活化能进行了确定 .结果表明 ,在弱电子偶合情况下 ,所提的精确与近似方案在确定溶液中电子自交换反应偶合矩阵元方面都是有效的 .尽管引入Newton近似稍微减小偶合矩阵元 ,但仍与精确法和其它理论法吻合较好 .此类体系偶合矩阵元一般较小 (<10 0cm-1) 。This paper presents several new theorectical schemes for experimentally determining electronic coupling matrix element of the self-exchange electron transfer reactions between the hydrated redox ion pairs in solution by using the experimental electron transfer rate data. The activation energies are determined by using a new potential function model proposed here in which the potential energy surfaces are obtained by fitting the relevant mono-specties ab initio data with an analytical function. Results have shown that the accurate and approximate schemes in the limit of weak electronic coupling are valid in determining the electron transfer coupling matrix element of the self-exchange reactions in solution. Although inclusion of the Newton approximation may slightly decrease the values of the coupling matrix element, they are still in good agreement with those from the accurate method and the other theoretical methods. The implication that the values of the coupling matrix element is small for these system (<100 cm -1 )is that the electron transfer reactions between the hydrated ion pairs in solution are nonadiabatic in nature.

关 键 词：电子交换反应 偶合矩阵元 溶液 水合离子 计算 

分 类 号：O645.164[理学—物理化学]