Autocatalysis due to combinatorial enhancement

Abstract

We demonstrate that autocatalytic reactions, where a product catalyzes its own formation, can be significantly accelerated when the product molecules are indistinguishable from each other. This ``combinatorial enhancement," analogous to the driving force of osmotic pressure, arises from the increased multiplicity of microscopic configurations. We quantify this effect with a free-energy gain, Fgain, and validate our theoretical predictions using molecular dynamics simulations. We also propose an experiment to directly test this phenomenon, potentially providing new insights into self-assembly, biomolecular binding, and other cooperative processes.