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Reaction rate calculation with time-dependent invariant manifolds

机译:时变不变流形的反应速率计算

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The identification of trajectories that contribute to the reaction rate is the crucial dynamical ingredient in any classical chemical reactivity calculation. This problem often requires a full scale numerical simulation of the dynamics, in particular if the reactive system is exposed to the influence of a heat bath. As an efficient alternative, we propose here to compute invariant surfaces in the phase space of the reactive system that separate reactive from nonreactive trajectories. The location of these invariant manifolds depends both on time and on the realization of the driving force exerted by the bath. These manifolds allow the identification of reactive trajectories simply from their initial conditions, without the need of any further simulation. In this paper, we show how these invariant manifolds can be calculated, and used in a formally exact reaction rate calculation based on perturbation theory for any multidimensional potential coupled to a noisy environment.
机译:在任何经典的化学反应性计算中,确定有助于反应速率的轨迹是至关重要的动力学因素。这个问题通常需要对动力学进行全面的数值模拟,特别是如果反应性系统暴露于热浴的影响下。作为一种有效的替代方法,我们在此建议在反应性系统的相空间中计算将反应性轨迹与非反应性轨迹分开的不变表面。这些不变的歧管的位置既取决于时间又取决于浴液施加的驱动力的实现。这些歧管可以简单地从其初始条件识别反应轨迹,而无需任何进一步的模拟。在本文中,我们展示了如何计算这些不变流形,并将其用于基于扰动理论的形式精确的反应速率计算,以用于耦合到嘈杂环境的任何多维电势。

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