溶液中外氛电子转移反应的电子传递系数的量子效应

QUANTUM EFFECTS ON ELECTRONIC TRANSMISSION COEFFICIENTS FOR OUTER_SPHERE ELECTRON EXCHANGE REACTION IN SOLUTION

用黄金规则和鞍点近似估算了电子转移速率的重要参数．考虑到量子效应对过渡金属氧化—还原的电子传递系数是重要的参量，采用了合适的光谱和光电发射数据，并根据已报导的电子耦合矩阵元的数据．得到了合理的结果，并与经典及量子力学理论进行了比较．结果表明对于室温下发生的此类反应，电子传递系数的值近似或低于１．量子效应使反应速率的绝对值增加了几倍。

The Golden rule and saddle point approximation are employed to evaluate the crucial parameters determining the electron transfer rate, electronic transmission coefficient quantitatively for electron exchange reactions involving transition-metal redox couples considering quantum effects. Adopting appropriate spectroscopic and photoemission data, and the reported value for electronic coupling matrix element, reasonable results are obtained and compared in term of classical and quantum mechanical theory. Investigation shows that for such reactions occurred at room temperature, the values for the electronic transmission coefficient are found to be less than or close to unity. The quantum effect increase the absolute rates by several times, which are not dramatic but still should be considered for complementary purpose.