Information Thermodynamics of the TransitionPath Ensemble
Abstract
The reaction coordinate describing a transition between reactant and product is a fundamental concept in the theory of chemical reactions. Within transitionpath 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 informationtheoretic 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.
 Publication:

Physical Review Letters
 Pub Date:
 April 2022
 DOI:
 10.1103/PhysRevLett.128.170602
 arXiv:
 arXiv:2106.11511
 Bibcode:
 2022PhRvL.128q0602L
 Keywords:

 Condensed Matter  Statistical Mechanics;
 Physics  Chemical Physics
 EPrint:
 10 pages, 2 figures