论文标题
过渡状态和纠缠群众行动法
Transition states and entangled mass action law
论文作者
论文摘要
（广义）质量作用定律（MAL）推导的经典方法假设中间过渡状态（i）的寿命很短，并且（ii）与基本反应的初始试剂处于部分平衡。部分平衡假设（II）意味着中间体的反向分解要比其通过其他通道向产品的过渡快得多。在这项工作中，我们证明了如何避免这种局部平衡假设改变反应速率。过渡状态理论的这种动力学修改导致反应速率的有效“纠缠”，成为不同表达式的线性组合。
The classical approaches to the derivation of the (generalized) Mass Action Law (MAL) assume that the intermediate transition state (i) has short life time and (ii) is in partial equilibrium with the initial reagents of the elementary reaction. The partial equilibrium assumption (ii) means that the reverse decomposition of the intermediates is much faster than its transition through other channels to the products. In this work we demonstrate how avoiding this partial equilibrium assumption modifies the reaction rates. This kinetic revision of transition state theory results in an effective `entanglement' of reaction rates, which become linear combinations of different MAL expressions.
