摘要
Marcus-Levich理论[1][2]是在研究电荷转移反应领域中的一个标志,但是无法解释在某些分子内电荷转移反应中盐效应能够减少电子转移速率2-3个数量级的现象。自由能表达式的推导[3]是基于一个非平衡自由能函数,文章明确定义了这个表达式中的反应坐标,并由反应扩散方程的解导出了速率常数依赖于反应坐标的时间相关函数。理论计算结果与实验数据相符,并且此理论也可以扩展到在离子液体中的电荷转移反应。
Marcus-Levich theory has set up a land mark in charge transfer reactions field.However,this does not explain the fact that salt effect can reduce the electron transfer rate in two to three orders since the sole consideration of the reorganization energy to the activation energy from ion atmosphere can not explain the salt effect on electron transfer rate.Free energy surfaces are derived based on a non equilibrium free energy functional.Reaction coordinates are clearly defined.The solution of the reaction diffusion equation leads to a rate constant depending on the time correlation function of the reaction coordinates time correlation function.The theory agrees fairly wellwith experiment.The theory can also be extended to charge-transfer in the ＂ionic fluids.＂
出处
《廊坊师范学院学报（自然科学版）》
2010年第6期73-75,共3页
Journal of Langfang Normal University(Natural Science Edition)
