Validity of path thermodynamic description of reactive systems: Microscopic simulations

TL;DR

This paper uses microscopic simulations to evaluate the validity of traditional path thermodynamics in reactive systems, confirming its applicability over recent alternative stochastic models.

Contribution

The study demonstrates that microscopic simulations support traditional stochastic modeling, challenging the validity of a new alternative approach.

Findings

Microscopic simulations confirm traditional path thermodynamics predictions.

Alternative stochastic modeling is invalidated by simulation results.

Results support the continued use of traditional models in reactive systems.

Abstract

Traditional stochastic modeling of reactive systems limits the domain of applicability of the associated path thermodynamics to systems involving a single elementary reaction at the origin of each observed change in composition. An alternative stochastic modeling has recently been proposed to overcome this limitation. These two ways of modeling reactive systems are in principle incompatible. The question thus arises about choosing the appropriate type of modeling to be used in practical situations. In the absence of sufficiently accurate experimental results, one way to address this issue is through the microscopic simulation of reactive fluids, usually based on hard-sphere dynamics in the Boltzmann limit. In this paper, we show that results obtained through such simulations unambiguously confirm the predictions of traditional stochastic modeling, invalidating a recently proposed alternative.