Articles | Volume 14, issue 22
Atmos. Chem. Phys., 14, 12023–12030, 2014
Atmos. Chem. Phys., 14, 12023–12030, 2014

Research article 17 Nov 2014

Research article | 17 Nov 2014

Methane sulfonic acid-enhanced formation of molecular clusters of sulfuric acid and dimethyl amine

N. Bork1,2, J. Elm2, T. Olenius1, and H. Vehkamäki1 N. Bork et al.
  • 1University of Helsinki, Department of Physics, Division of Atmospheric Sciences, P. O. Box 64, 00014 Helsinki, Finland
  • 2University of Copenhagen, Department of Chemistry, Universitetsparken 5, 2100, Copenhagen, Denmark

Abstract. Over oceans and in coastal regions, methane sulfonic acid (MSA) is present in substantial concentrations in aerosols and in the gas phase. We present an investigation into the effect of MSA on sulfuric acid- and dimethyl amine (DMA)-based cluster formation rates. From systematic conformational scans and well-tested ab initio methods, we optimise the structures of all MSAx (H2SO4)yDMAz clusters where x + y ≤ 3 and z ≤ 2. The resulting thermodynamic data are used in the Atmospheric Cluster Dynamics Code, and the effect of MSA is evaluated by comparing ternary MSA–H2SO4–DMA cluster formation rates to binary H2SO4–DMA cluster formation rates. Within the range of atmospherically relevant MSA concentrations, we find that MSA may increase cluster formation rates by up to 1 order of magnitude, although typically, the increase will be less than 300 % at 258 K, less than 100 % at 278 K and less than 15 % at 298 K. The results are rationalised by a detailed analysis of the main growth paths of the clusters. We find that MSA-enhanced clustering involves clusters containing one MSA molecule, while clusters containing more than one MSA molecule do not contribute significantly to the growth.

Final-revised paper