Effect of Bisulfate, Ammonia, and Ammonium on the Clustering of Organic Acids and Sulfuric Acid

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Myllys , N L P , Olenius , T M , Kurten , T C , Vehkamäki , H T K , Riipinen , I & Elm , J 2017 , ' Effect of Bisulfate, Ammonia, and Ammonium on the Clustering of Organic Acids and Sulfuric Acid ' , Journal of Physical Chemistry A , vol. 121 , no. 25 , pp. 4812–4824 . https://doi.org/10.1021/acs.jpca.7b03981

Title: Effect of Bisulfate, Ammonia, and Ammonium on the Clustering of Organic Acids and Sulfuric Acid
Author: Myllys, Nanna Laura Pauliina; Olenius, Tinja Marjatta; Kurten, Theo Christian; Vehkamäki, Hanna Tuula Katariina; Riipinen, Ilona; Elm, Jonas
Other contributor: University of Helsinki, Department of Physics
University of Helsinki, Stockholm University
University of Helsinki, Department of Chemistry
University of Helsinki, Department of Physics
University of Helsinki, Department of Physics

Date: 2017-06-06
Language: eng
Number of pages: 13
Belongs to series: Journal of Physical Chemistry A
ISSN: 1089-5639
DOI: https://doi.org/10.1021/acs.jpca.7b03981
URI: http://hdl.handle.net/10138/299814
Abstract: We investigate the effect of the bisulfate anion HSO4-, ammonium cation NH4+, and ammonia NH3 on the clustering of sulfuric acid and pinic acid or 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA). The systems were chosen based on their expected relevance in atmospheric new particle formation. Using quantum chemical methods together with kinetic calculations, we study the ability of these compounds to enhance cluster formation and growth. The cluster structures are obtained and frequencies are calculated using three different DFT functionals (M06-2X, PW91, and omega B97X-D) with the 6-31++G(d,p) basis set. The electronic energies are corrected using an accurate DLPNO-CCSD(T)/def2-QZVPP level of theory. The evaporation rates are evaluated based on the calculated Gibbs free energies. The interaction between the ions and sulfuric acid or carboxylic acid group is strong, and thereby small two-component ionic clusters are found to be very stable against evaporation. The presence of bisulfate stimulates the cluster formation through addition of the sulfuric acid, whereas the presence of ammonium favors the addition of organic acids. Bisulfate and ammonium enhance the first steps of cluster formation; however, at atmospheric conditions further cluster growth is limited due to the weak interaction and fast evaporation of the larger three-component clusters. On the basis of our results it is therefore unlikely that the studied organic acids and sulfuric acid, even together with bisulfate, ammonia, or ammonium can drive new-particle formation via clustering mechanisms. Other mechanisms such as chemical reactions are needed to explain observed new-particle formation events in the presence of oxidized organic compounds resembling the acids studied here.
Subject: 114 Physical sciences
116 Chemical sciences
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