Cylindrical manifolds and reactive island kinetic theory in the time domain
Cylindrical manifolds and reactive island kinetic theory in the time domain
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时域圆柱流形和反应岛动力学理论
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发表时间：
1992
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通讯作者：
N. D. Leon
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作者：
N. D. Leon
在最近的一系列出版物中，我们讨论了圆柱形流形的概念及其在调节化学反应的反应动力学中的作用。圆柱形流形用于发展化学反应速率理论，我们称之为反应岛(RI)理论。RI理论是根据n个Poincare映射平面之间的映射动力学来决定的--这被称为“n-映射”。因此，‘’time‘’没有明确地出现在n-map RI理论中。在本文中，我们将n-MAP RI理论扩展到时间域。形式理论，作为一个主方程，被用来获得时间RI模型。将时间RI理论应用于具有动力学混沌的两自由度系统。将时间RI理论的结果与经典的莱斯-拉姆斯伯格-卡塞尔-马库斯(RRKM)理论进行了比较，发现即使在假定的“理想”动力学条件下，RRKM理论也可能与数值模拟存在严重的误差。也可以看到，时态RI理论准确地解释了...
In a series of recent publications we discussed the concept of cylindrical manifolds and their role in mediating the reaction dynamics of chemical reactions. The cylindrical manifolds were used to develop a chemical reaction rate theory we called reactive island (RI) theory. RI theory was cast in terms of the map dynamics between n Poincare mapping planes—which were referred to as the ‘‘n‐map.’’ Therefore ‘‘time’’ did not explicitly appear within n‐map RI theory. In this paper we extend n‐map RI theory to the time domain. The formal theory, cast as a master equation, is used to obtain the temporal RI model. Temporal RI theory is applied to a two degree‐of‐freedom system exhibiting dynamical chaos. The results of temporal RI theory are compared with classical Rice–Ramsberger–Kassel–Marcus (RRKM) theory and it is found that even under, presumably, ‘‘ideal’’ dynamical conditions, RRKM theory can be in serious error with numerical simulation. It is also seen that temporal RI theory accurately accounts for the...