The driving effects of common atmospheric molecules for formation of clusters: the case of sulfuric acid, nitric acid, hydrochloric acid, ammonia, and dimethylamine

Abstract

Understanding how secondary aerosols form in the atmosphere is one of the main uncertainties for a better understanding of global warming. Secondary aerosols form from gas-phase molecules that combine to create prenucleation complexes, which can then grow to form aerosols. The study of the formation of prenucleation complexes is difficult from both an experimental and theoretical point of view. Sulfuric acid has been linked to the formation of aerosols, yet the details of interactions are not understood. We have completed an exhaustive study of the formation of prenucleation complexes of three strong acids: sulfuric acid, nitric acid, and hydrochloric acid, combined with ammonia and dimethylamine bases, and three water molecules. By combining an evolutionary algorithm search routine with density functional geometry optimizations and single-point electronic energy calculations with complete basis set (CBS) extrapolations, we have completed an exhaustive search of the DLPNO-CCSD(T)/CBS//ωB97X-D/6-31++G** Gibbs free energy surface for this system. We have used previous work where the weaker formic acid replaces either nitric acid or hydrochloric acid to explore the details of how three acids combine with two bases and a few water molecules to make prenucleation clusters. As clusters grow, stabilizing effects of nitric acid, hydrochloric acid, and formic acid change in unique ways. This research adds to the body of work that illustrates that, depending on the system being studied, the acid/base strength of the monomers, the charge distribution within the clusters, and the detailed hydrogen bond topology have a subtle interplay that determines which cluster is most stable.