Phase-space reaction network on a multisaddle energy landscape: HCN isomerization.
Phase-space reaction network on a multisaddle energy landscape: HCN isomerization.
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DOI：
10.1063/1.2044707
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发表时间：
2005-11
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影响因子：
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通讯作者：
Chun-Biu Li;Y. Matsunaga;M. Toda;T. Komatsuzaki
中科院分区：
文献类型：
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作者：
Chun-Biu Li;Y. Matsunaga;M. Toda;T. Komatsuzaki
通过使用 HCN/CNH 异构化反应作为多鞍能量景观上化学反应的说明性载体，我们给出了与相空间中直通反应管相关的分子运动的明确可视化，在该相空间内，所有反应轨迹从一个盆地传递到另一个盆地，消除了构型空间中的重新交叉轨迹。这种可视化为我们提供了化学直觉，了解化学物质如何沿着多维相空间中的反应速率斜率与构型空间中的固有反应路径“行走”。两个不同的 HCN 和 CNH 井中不同的非遍历特征可以通过这些潜在极小值中的庞加莱曲面截面轻松证明，它先验地预测了位于势井中的轨迹模式。我们阐明了引起非马尔可夫动力学或连续多鞍化学反应的动力学相关性的全局相空间结构。还讨论了与化学反应中产物状态的可控性相关的相空间结构。
By using the HCN/CNH isomerization reaction as an illustrative vehicle of chemical reactions on multisaddle energy landscapes, we give explicit visualizations of molecular motions associated with a straight-through reaction tube in the phase space inside which all reactive trajectories pass from one basin to another, with eliminating recrossing trajectories in the configuration space. This visualization provides us with a chemical intuition of how chemical species "walk along" the reaction-rate slope in the multidimensional phase space compared with the intrinsic reaction path in the configuration space. The distinct nonergodic features in the two different HCN and CNH wells can be easily demonstrated by a section of Poincare surface of section in those potential minima, which predicts in a priori the pattern of trajectories residing in the potential well. We elucidate the global phase-space structure which gives rise to the non-Markovian dynamics or the dynamical correlation of sequential multisaddle chemical reactions. The phase-space structure relevant to the controllability of the product state in chemical reactions is also discussed.