Information Thermodynamics of the Transition-Path Ensemble

Area of Science:

• Chemical Physics
• Physical Chemistry
• Reaction Dynamics

Background:

• The reaction coordinate is crucial for understanding chemical transitions.
• Transition-path theory defines the committor as a quantitative reaction coordinate.
• The committor quantifies the probability of reaching the product before the reactant.

Purpose of the Study:

• To establish an information-theoretic foundation for the committor function.
• To demonstrate the relationship between entropy production and information generation in reactive trajectories.
• To identify optimal reaction coordinates based on information theory.

Main Methods:

• Developing an information-theoretic framework for the committor.
• Analyzing entropy production in transition path sampling.
• Calculating dynamical information generated by system trajectories.

Main Results:

• An information-theoretic origin for the committor was established.
• Entropy production during transition path selection was shown to equal the dynamical information about reactivity.
• This equality holds for arbitrary coordinates, with the committor being optimal.

Conclusions:

• The committor provides an information-theoretic measure of reaction coordinate relevance.
• Entropy production and information generation are fundamentally linked in reactive systems.
• This framework offers new insights into quantifying chemical reactivity and reaction pathways.