Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A1S6, Canada.
Department of Physics, Simon Fraser University, Burnaby, British Columbia V5A1S6, Canada.
Phys Rev Lett. 2022 Apr 29;128(17):170602. doi: 10.1103/PhysRevLett.128.170602.
The reaction coordinate describing a transition between reactant and product is a fundamental concept in the theory of chemical reactions. Within transition-path theory, a quantitative definition of the reaction coordinate is found in the committor, which is the probability that a trajectory initiated from a given microstate first reaches the product before the reactant. Here we develop an information-theoretic origin for the committor and show how selecting transition paths from a long ergodic equilibrium trajectory induces entropy production which exactly equals the information that system dynamics provide about the reactivity of trajectories. This equality of entropy production and dynamical information generation also holds at the level of arbitrary individual coordinates, providing parallel measures of the coordinate's relevance to the reaction, each of which is maximized by the committor.
描述反应物和产物之间转变的反应坐标是化学反应理论中的一个基本概念。在过渡态理论中，反应坐标的定量定义可以在“牵连度”中找到，它是从给定微观态开始的轨迹首先到达产物而不是反应物的概率。在这里，我们从信息论的角度发展了牵连度的起源，并展示了如何从长的遍历平衡轨迹中选择过渡路径，从而导致熵产生，其正好等于系统动力学对轨迹反应性的信息。这种熵产生和动力学信息生成的相等性也适用于任意单个坐标的水平，为坐标与反应的相关性提供了平行的度量，每个度量都由牵连度最大化。
