Role of base strength, cluster structure and charge in sulfuric-acid-driven particle formation

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Myllys , N , Kubecka , J , Besel , V , Alfaouri , D , Olenius , T , Smith , J N & Passananti , M 2019 , ' Role of base strength, cluster structure and charge in sulfuric-acid-driven particle formation ' , Atmospheric Chemistry and Physics , vol. 19 , no. 15 , pp. 9753-9768 . https://doi.org/10.5194/acp-19-9753-2019

Title: Role of base strength, cluster structure and charge in sulfuric-acid-driven particle formation
Author: Myllys, Nanna; Kubecka, Jakub; Besel, Vitus; Alfaouri, Dina; Olenius, Tinja; Smith, James Norman; Passananti, Monica
Contributor: University of Helsinki, INAR Physics
University of Helsinki, INAR Physics
University of Helsinki, INAR Physics
University of Helsinki, INAR Physics
University of Helsinki, Institute for Atmospheric and Earth System Research (INAR)
Date: 2019-08-02
Number of pages: 16
Belongs to series: Atmospheric Chemistry and Physics
ISSN: 1680-7324
URI: http://hdl.handle.net/10138/305920
Abstract: In atmospheric sulfuric-acid-driven particle formation, bases are able to stabilize the initial molecular clusters and thus enhance particle formation. The enhancing potential of a stabilizing base is affected by different factors, such as the basicity and abundance. Here we use weak (ammonia), medium strong (dimethylamine) and very strong (guanidine) bases as representative atmospheric base compounds, and we systematically investigate their ability to stabilize sulfuric acid clusters. Using quantum chemistry, we study proton transfer as well as intermolecular interactions and symmetry in clusters, of which the former is directly related to the base strength and the latter to the structural effects. Based on the theoretical cluster stabilities and cluster population kinetics modeling, we provide molecular-level mechanisms of cluster growth and show that in electrically neutral particle formation, guanidine can dominate formation events even at relatively low concentrations. However, when ions are involved, charge effects can also stabilize small clusters for weaker bases. In this case the atmospheric abundance of the bases becomes more important, and thus ammonia is likely to play a key role. The theoretical findings are validated by cluster distribution experiments, as well as comparisons to previously reported particle formation rates, showing a good agreement.
Subject: 114 Physical sciences
GUANIDINO COMPOUNDS
NUCLEATION
GROWTH
DIMETHYLAMINE
AMMONIA
AMINES
NANOPARTICLES
METHYLAMINE
DIAMINES
IONS
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