Free energy barrier in the growth of sulfuric acid–ammonia and sulfuric acid–dimethylamine clusters

Abstract

The first step in atmospheric new particle formation involves the aggregation of gas phase molecules into small molecular clusters that can grow by colliding with gas molecules and each other. In this work we used first principles quantum chemistry combined with a dynamic model to study the steady-state kinetics of sets of small clusters consisting of sulfuric acid and ammonia or sulfuric acid and dimethylamine molecules. Both sets were studied with and without electrically charged clusters. We show the main clustering pathways in the simulated systems together with the quantum chemical Gibbs free energies of formation of the growing clusters. In the sulfuric acid-ammonia system, the major growth pathways exhibit free energy barriers, whereas in the acid-dimethylamine system the growth occurs mainly via barrierless condensation. When ions are present, charged clusters contribute significantly to the growth in the acid-ammonia system. For dimethylamine the role of ions is minor, except at very low acid concentration, and the growing clusters are electrically neutral.