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Communication: Transition state theory for dissipative systems without a dividing surface

机译:交流:无分界面的耗散系统的过渡态理论

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Transition state theory is a central cornerstone in reaction dynamics. Its key step is the identification of a dividing surface that is crossed only once by all reactive trajectories. This assumption is often badly violated, especially when the reactive system is coupled to an environment. The calculations made in this way then overestimate the reaction rate and the results depend critically on the choice of the dividing surface. In this Communication, we study the phase space of a stochastically driven system close to an energetic barrier in order to identify the geometric structure unambiguously determining the reactive trajectories, which is then incorporated in a simple rate formula for reactions in condensed phase that is both independent of the dividing surface and exact.
机译:过渡态理论是反应动力学的核心基石。它的关键步骤是识别所有反应轨迹仅相交一次的分隔面。通常会严重违反该假设,特别是当反应系统耦合到环境时。然后,以这种方式进行的计算高估了反应速率,结果主要取决于分隔表面的选择。在本交流中,我们研究靠近高能势垒的随机驱动系统的相空间,以便明确确定确定反应轨道的几何结构,然后将其合并到一个简单的速率公式中,以计算凝聚相中的反应。分割面的精确度。

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