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反应界面的稳健存在决定了化学反应的命运。

Robust existence of a reaction boundary to separate the fate of a chemical reaction.

机构信息

Molecule and Life Nonlinear Sciences Laboratory, Research Institute for Electronic Science, Hokkaido University, Kita 20 Nishi 10, Kita-ku, Sapporo 001-0020, Japan.

出版信息

Phys Rev Lett. 2010 Jul 23;105(4):048304. doi: 10.1103/PhysRevLett.105.048304. Epub 2010 Jul 21.

Abstract

Nonlinear dynamics around a rank-one saddle is investigated in a high energy regime above the reaction threshold. The transition state (TS) is considered as a surface of a "point of no return" through which all reactive trajectories pass only once in the process of climbing over the saddle before being captured in the product state. A no-return TS ceases to exist above a certain high energy regime. However, even at high energies where the no-return TS can no longer exist, it is shown that "an impenetrable barrier" in the phase space robustly persists, which acts as a boundary between reactive and nonreactive trajectories. This implies that we can yet predict the fate of reactions even when the no-return TS may not exist. As an example, we show the analysis of dynamical systems theory for a hydrogen atom in crossed electric and magnetic fields.

摘要

在反应阈以上的高能区研究了一级鞍点周围的非线性动力学。过渡态(TS)被认为是一个“不归点”的表面,所有反应轨迹在攀过鞍点进入产物态之前,在这个过程中只能通过一次。在某个高能区以上,不归点 TS 不再存在。然而,即使在不归点 TS 不再存在的高能区,也表明在相空间中仍然存在一个“不可穿透的屏障”,它作为反应和非反应轨迹之间的边界。这意味着,即使不归点 TS 可能不存在,我们仍然可以预测反应的命运。作为一个例子,我们展示了在交叉电场和磁场中氢原子的动力学系统理论分析。

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