A termolecular reaction theory for gas-phase nucleation based on long-range intermolecular forces

Abstract

The birth of a new phase is usually described thermodynamically, but in the gas phase it begins as chemistry. Here, we show that gas-phase nucleation can be described as a termolecular reaction network controlled primarily by long-range intermolecular forces. In single-component mixtures, dimer formation emerges as a direct termolecular process, whereas in binary mixtures a chaperon mechanism can enhance nucleation, with the second component acting as a catalyst for cluster formation. By incorporating cluster evaporation, the same framework can be extended beyond the collision limit, providing a molecular route to nucleation in regimes where larger critical clusters become relevant. We test the theory against unary and binary nucleation of water, toluene, and butane, obtaining agreement in absolute rates within one order of magnitude across the explored temperature and density ranges. These results identify long-range intermolecular forces as molecular drivers of gas-phase nucleation and establish elementary termolecular chemistry as a predictive route to cluster formation.