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Reactions between hydroxyl-substituted alkylperoxy radicals and Criegee intermediates: Correlations of the electronic characteristics of methyl substituents and the reactivity

Abstract

The reactions of four hydroxyl-substituted alkylperoxy (RO2) radicals with four stabilized Criegee intermediates (SCIs) were investigated. Due to the existence of various reactive sites in both RO2 and SCI, various reaction modes were obtained. By adjusting the relative orientation of the two components of the reactants, different pathways were predicted. The addition of RO2 radical terminal oxygen atom to SCI carbonyl carbon is the most accessible reaction mode. For the RO2 radicals, increasing the number of methyl substituent in β-carbon will promote the addition reaction. Carbonyl oxides with hydrogen atoms as substituents in the anti-position react faster than the corresponding carbonyl oxides with the hydrogen atom substituents in syn. Thus, the reaction barrier can be “tuned” by the substitution of alkyl groups. The analysis of the transition states reveals that there are correlations between the reaction barrier heights, the NPA charges and the electron spin population of terminal oxygen of RO2, as well as that with the interatomic distances of O-C in transition states. As the oligomers formed by the sequential addition of SCIs to RO2 radicals are the common components of secondary organic aerosols, the investigation has a contribution to understanding the formation of SOA.

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Publication details

The article was received on 09 Feb 2017, accepted on 15 May 2017 and first published on 16 May 2017


Article type: Paper
DOI: 10.1039/C7CP00869D
Citation: Phys. Chem. Chem. Phys., 2017, Accepted Manuscript
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    Reactions between hydroxyl-substituted alkylperoxy radicals and Criegee intermediates: Correlations of the electronic characteristics of methyl substituents and the reactivity

    Q. Zhao, F. Liu, W. Wang, C. Li, J. Lu and W. Wang, Phys. Chem. Chem. Phys., 2017, Accepted Manuscript , DOI: 10.1039/C7CP00869D

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