Transition states and entangled mass action law

TL;DR

This paper revises classical transition state theory by removing the partial equilibrium assumption, revealing an entangled form of reaction rates as linear combinations of different mass action law expressions.

Contribution

It introduces a kinetic modification to transition state theory that accounts for non-equilibrium intermediates, leading to entangled reaction rate expressions.

Findings

Reaction rates become linear combinations of MAL expressions.

Avoiding partial equilibrium alters the classical reaction rate derivation.

The new theory captures more complex reaction dynamics.

Abstract

The classical approaches to the derivation of the (generalized) Mass Action Law (MAL) assume that the intermediate transition state (i) has short life time and (ii) is in partial equilibrium with the initial reagents of the elementary reaction. The partial equilibrium assumption (ii) means that the reverse decomposition of the intermediates is much faster than its transition through other channels to the products. In this work we demonstrate how avoiding this partial equilibrium assumption modifies the reaction rates. This kinetic revision of transition state theory results in an effective `entanglement' of reaction rates, which become linear combinations of different MAL expressions.