Cylindrical manifolds in phase space as mediators of chemical reaction dynamics and kinetics. I. Theory
Cylindrical manifolds in phase space as mediators of chemical reaction dynamics and kinetics. I. Theory
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相空间中的圆柱形流形作为化学反应动力学和动力学的媒介。
DOI：
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发表时间：
1991
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通讯作者：
R. Q. Topper
中科院分区：
文献类型：
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作者：
N. D. Leon;M. Mehta;R. Q. Topper
建立了基于相空间结构的反应微正则动力学理论。研究表明，反应跨越能垒的动力学是由嵌入相空间的具有简单圆柱体几何形状的不变流形来调节的。这些想法是通过考虑由两个振动自由度（反应坐标和“浴”坐标）建模的分子系统而发展起来的。动力学理论是通过关注n个映射平面（“n - map”）和其中的“反应岛”（RI）结构之间的动力学来构建的。我们讨论了如何从RI动力学模型得到异构化反应中构象居群衰变的结构。讨论了动力学方程的形式解，特别注意了异构化反应速率的计算。形式理论在本系列的第一篇论文中得到了发展。模型分子体系反应动力学的数值考虑及应用
A microcanonical kinetic theory of reactions based upon the structure within phase space is developed. It is shown that the dynamics of reaction across an energetic barrier is mediated by invariant manifolds embedded in phase space that have the geometry of simple cylinders. The ideas are developed by considering molecular systems modeled by two vibrational degrees of freedom, a reaction coordinate and a ‘‘bath’’ coordinate. The kinetic theory is constructed by focusing on the dynamics between n mapping planes (‘‘n‐map’’) and the ‘‘reactive island’’ (RI) structure within them. We discuss how the structure of the conformer population decay in isomerization reactions can be obtained from the RI kinetic model. Formal solutions of the kinetic equations are discussed with specific attention given towards the calculation of the isomerization reaction rate. The formal theory is developed in Paper I of this series. Numerical considerations and applications to the reaction dynamics of model molecular systems with ...