Contribution of Methanesulfonic Acid to the Formation of Molecular Clusters in the Marine Atmosphere
Freja Rydahl Rasmussen, Jakub Kubečka, Jonas Elm
Abstract
Because of the lack of long-term measurements, new particle formation (NPF) in the marine atmosphere remains puzzling. Using quantum chemical methods, this study elucidates the cluster formation and further growth of sulfuric acid–methanesulfonic acid–dimethylamine (SA-MSA-DMA) clusters, relevant to NPF in the marine atmosphere. The cluster structures and thermochemical parameters of (SA)n(MSA)m(DMA)l (n + m ≤ 4 and l ≤ 4) systems are calculated using density functional theory at the ωB97X-D/6-31++G(d,p) level of theory, and the single-point energies are calculated using high-level DLPNO-CCSD(T0)/aug-cc-pVTZ calculations. The calculated thermochemistry is used as input to the Atmospheric Cluster Dynamics Code (ACDC) to gain insight into the cluster dynamics. At ambient conditions (298.15 K, 1 atm), we find that the distribution of outgrowing clusters primarily consists of SA and DMA, with a minor contribution from the mixed SA–MSA–DMA clusters. At lower temperature (278.15 K, 1 atm) the distribution broadens, and clusters containing one or more MSA molecules emerge. These findings show that in the cold marine atmosphere MSA likely participates in atmospheric NPF.