Closed-Shell Organic Compounds Might Form Dimers at the Surface of Molecular Clusters

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Hirvonen , V , Myllys , N , Kurtén , T & Elm , J 2018 , ' Closed-Shell Organic Compounds Might Form Dimers at the Surface of Molecular Clusters ' , Journal of Physical Chemistry A , vol. 122 , no. 6 , pp. 1771-1780 . https://doi.org/10.1021/acs.jpca.7b11970

Title: Closed-Shell Organic Compounds Might Form Dimers at the Surface of Molecular Clusters
Author: Hirvonen, Viivi; Myllys, Nanna; Kurtén, Theo; Elm, Jonas
Contributor organization: Department of Physics
Department of Chemistry
Date: 2018-02-15
Language: eng
Number of pages: 10
Belongs to series: Journal of Physical Chemistry A
ISSN: 1089-5639
DOI: https://doi.org/10.1021/acs.jpca.7b11970
URI: http://hdl.handle.net/10138/271658
Abstract: The role of covalently bound dimer formation is studied using highlevel quantum chemical methods. Reaction free energy profiles for dimer formation between common oxygen-containing functional groups are calculated, and based on the Gibbs free energy differences between transition states and reactants, we show that none of the studied two-component gas-phase reactions are kinetically feasible at 298.15 K and 1 atm. Therefore, the catalyzing effect of water, base, or acid molecules is calculated, and sulfuric acid is identified to lower the activation free energies significantly. We find that the reactions yielding hemiacetal, peroxyhemiacetal, alpha-hydroxyester, and geminal diol products occur with activation free energies of less than 10 kcal/mol with sulfuric acid as a catalyst, indicating that these reactions could potentially take place on the surface of sulfuric acid clusters. Additionally, the formed dimer products bind stronger onto the pre-existing cluster than the corresponding reagent monomers do. This implies that covalent dimerization reactions stabilize the existing cluster thermodynamically and make it less likely to evaporate. However, the studied small organic compounds, which contain only one functional group, not able to form dimer are products that are stable against evaporation at atmospheric conditions. Calculations of dimer formation onto a cluster surface and the clustering ability of dimer products should be extended to large terpene oxidation products in order to estimate the real atmospheric significance.
Subject: 114 Physical sciences
AUTOXIDATION PRODUCT C6H8O7
DENSITY-FUNCTIONAL THEORY
SULFURIC-ACID
ATMOSPHERIC IMPLICATIONS
ALPHA-PINENE
ACCRETION REACTIONS
PARTICULATE MATTER
ORBITAL METHODS
OXALIC-ACID
BASIS-SETS
116 Chemical sciences
Peer reviewed: Yes
Usage restriction: openAccess
Self-archived version: acceptedVersion


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