What Is Required for Highly Oxidized Molecules To Form Clusters with Sulfuric Acid?

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Abstract
We have studied the specific requirements of a given neutral organic molecule to act as a stabilizer in sulfuric acid induced new particle formation. Based on an analysis of the reaction Gibbs free energies between simple functional groups and sulfuric acid, carboxylic acid groups are identified to show the strongest hydrogen bonding interaction with sulfuric acid. The free energy associated with the hydrogen bonding between sulfuric acid and 14 different carboxylic acids of atmospheric relevance reveal that the binding strength is very dependent on the ability of sulfuric acid to form an additional hydrogen bond via its vacant S–OH group to a γ-carbonyl group in the organic molecule. Extending the analysis to monoterpene oxidation products and further to large dimer esters, we identify the following necessary criteria for a given organic oxidation product to efficiently stabilize sulfuric acid clustering: (1) weak or no intramolecular hydrogen bonds in the isolated monomer; (2) more than two carboxylic acid groups. As a proof of concept we show that these requirements correspond to the docking of a sulfuric acid molecule between two non-interacting carboxylic acid groups in the organic molecule. These findings suggests that, for a given organic oxidation product to participate in the initial steps in new particle formation involving sulfuric acid, very distinct molecular features are required.
Funding Information
  • Suomen Akatemia
  • Carlsbergfondet
  • H2020 European Research Council (692891)

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