Theoretical analysis of sulfuric acid–dimethylamine–oxalic acid–water clusters and implications for atmospheric cluster formation

Abstract

In recent years, organic compounds potentially involved in atmospheric particle formation have received increased attention. However, the contributions of organic acids as precursors in nucleation remain ambiguous. In this study, the low-lying structures and thermodynamics of the sulfuric acid–dimethylamine–oxalic acid–water system are obtained at the M06-2X/6-311+G(2d,p) level, and the single point energy of the clusters has been calculated at the DF-LMP2-F12/VDZ-F12 level. The formations of the multicomponent clusters are predicted based on thermodynamics, involving proton transfer and hydrogen bonding interactions. Oxalic acid can synergistically promote the formation of the sulfuric acid–dimethylamine–oxalic acid–water system while inhibiting this with the addition of more sulfuric acid molecules. The results of hydrate distribution show that un-hydrate clusters play a dominant role during formation. Moreover, dimethylamine and oxalic acid have similar effects on Rayleigh scattering properties, and the clusters involving complex mixtures of compounds can have high optical activities.