Transition states and entangled mass action law

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.