Department of Chemistry, University of Kansas, Lawrence, Kansas 66045, USA.
J Phys Chem B. 2010 Jun 10;114(22):7535-42. doi: 10.1021/jp911740c.
Nonadiabatic effects on the reaction rate constant of a model phenol-amine proton transfer system in a nanoconfined solvent have been investigated by employing classical mapping in conjunction with a reactive flux approach. It is observed that allowing nonadiabatic transitions makes the transition state more accessible thermodynamically but decreases the reactive flux due to increased transition state recrossing, resulting in an overall reduction in the rate constant by more than a factor of 2. The physical origins of these features are discussed.
非绝热效应对模型酚胺质子转移体系在纳米受限溶剂中反应速率常数的影响通过采用经典映射结合反应通量方法进行了研究。结果表明，允许非绝热跃迁使过渡态在热力学上更容易接近，但由于过渡态重交叉增加，反应通量减小，导致速率常数总体降低超过 2 倍。讨论了这些特征的物理起源。
