从MD得到平衡时基元反应速率常数的形式：热动力学的框架和建议
The form of the rate constant for elementary reactions at equilibrium from MD: framework and proposals for thermokinetics
摘要：
在一个基本的从头算化学反应中研究了具有滞后行为的二聚体反应的生成速率和浓度分布，其中滞后结构排除了具有预平衡和内部子反应的过渡态的形成.据发现，反应性系数，定义为从零密度速率常数的前向和后向步骤的偏离的措施有一个比率，等于活性系数比的产品和反应物的物种。从上述观察出发，借助于热力学中一些已证明的基本定理，发展了一种理论，并导出了表达式，由此可以得到一种从速率常数确定活度系数的可行的实验和计算方法。所发展的理论应用于离子反应，其中标准的Bronsted-Bjerrum速率方程及其例外情况被合理化，并且通过将离子缔合看作是一个n-mer过程，原则上可以在不同的适用假设下确定离子活度系数。
英文摘要：
The rates or formation and concentration distributions of a dimer reaction showing hysteresis behavior are examined in an ab initio chemical reaction designed as elementary and where the hysteresis structure precludes the formation of transition states (TS) with pre-equilibrium and internal sub-reactions. It was discovered that the the reactivity coefficients, defined as a measure of departure from the zero density rate constant for the forward and backward steps had a ratio that was equal to the activity coefficient ratio for the product and reactant species. From the above observations, a theory is developed with the aid of some proven elementary theorems in thermodynamics, and expressions are derived whereby a feasible experimental and computational method for determining the activity coefficients from the rate constants may be obtained The theory developed is applied to ionic reactions where the standard Bronsted-Bjerrum rate equation and exceptions to this are rationalized, and by viewing ion association as a n-meric process, ion activity coefficients may in principle be determined under varying applicable assumptions.
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