Geometric Investigation of Association/Dissociation Kinetics with an Application to the Master Equation for CH3 + CH3 ↔ C2H6
Geometric Investigation of Association/Dissociation Kinetics with an Application to the Master Equation for CH3 + CH3 ↔ C2H6
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DOI：
10.1021/jp014136a
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发表时间：
2002-05
影响因子：
2.9
通讯作者：
A. M. Davis;S. Klippenstein
中科院分区：
文献类型：
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作者：
A. M. Davis;S. Klippenstein
结合/解离动力学的动力学进行了研究，与标题反应的应用。重点是几何的相空间的唯象速率定律，林德曼机制，和主方程的可逆反应，所有这些都是非线性的。结果表明，这三个系统具有相似的相空间结构，包括一维流形。这个1-D流形描述了无论是解离或重组的渐近运动，是相应的特征向量的线性主方程描述解离没有重组的模拟。1-D流形允许从瞬态行为中分离渐近运动，并且与相空间中的其他流形一起允许更好地理解解离和重组过程。1-D流形还允许我们测试过去用于从主方程和林德曼机制计算缔合速率常数的各种近似，并开发新的方法。
The dynamics of association/dissociation kinetics is studied, with an application to the titled reaction. The focus is the geometry of the phase space of the phenomenological rate law, a Lindemann mechanism, and the master equation of this reversible reaction, all of which are nonlinear. It is shown that all three systems possess similar phase space structure, including a 1-D manifold. This 1-D manifold describes asymptotic motion for either dissociation or recombination and is the analogue of the corresponding eigenvector for linear master equations describing dissociation without recombination. The 1-D manifold allows for the separation of asymptotic motion from transient behavior and together with other manifolds in phase space allows a better understanding of the dissociation and recombination processes. The 1-D manifold also allows us to test various approximations that have been used in the past to calculate association rate constants from the master equation and Lindemann mechanism and develop new ...