Hydrogen-Bonding Interaction in Molecular Complexes and Clusters of Aerosol Nucleation Precursors

Complexes and clusters bridge the gap between molecular and macroscopic levels by linking individual gaseous molecules to newly formed nanoparticles but the driving forces and mechanism for the formation of complexes and clusters in the atmosphere are not well understood. We have performed ab initio and density functional quantum chemical calculations to elucidate the role of organic acids in the formation of complexes with common atmospheric nucleating precursors such as sulfuric acid, water, and ammonia. A central feature of the complexes is the presence of two hydrogen bonds. Organic acid-sulfuric acid complexes show one strong and one medium-strength hydrogen bond whereas the corresponding hydrogen bonds in organic acid-ammonia complexes are characterized as medium-strength and weak. The formation of strong hydrogen bonds in organic acid-sulfuric acid complexes is explained by the well-established resonance-assisted hydrogen bonding theory. Organic acid-sulfuric acid and organic acid-organic acid complexes possess the largest binding energies among the homomolecular and heteromolecular dimers, about 18 kcal mol(-1) from the composite theoretical methods. Topological analysis employing quantum theory of atoms in molecules (QTAIM) shows that the charge density and the Laplacian at bond critical points (BCPs) of the hydrogen bonds of the organic acid-sulfuric acid complex (e.g., benzoic acid-sulfuric acid and cis-pinonic acid-sulfuric acid) are 0.07 and 0.16 au, respectively, which falls in or exceeds the range of one strong and one medium-strength hydrogen bonding criteria.