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An extended computational study of Criegee intermediate - alcohol reactions

Watson, Nathan A. I., Black, Joshua A., Stonelake, Thomas M., Knowles, Peter J. ORCID: and Beames, Joseph M ORCID: 2019. An extended computational study of Criegee intermediate - alcohol reactions. Journal of Physical Chemistry A 123 (1) , pp. 218-229. 10.1021/acs.jpca.8b09349

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High level ab initio calculations (DF-LCCSD(T)-F12a//B3LYP/aug-cc-pVTZ) are performed on a range of stabilized Criegee intermediate (sCI) – alcohol reactions, computing reaction coordinate energies, leading to the formation of α-alkyoxyl-alkyl-hydroperoxides (AAAHs). These potential energy surfaces are used to model bimolecular reaction kinetics over a range of temperatures. The calculations performed in this work reproduce the complicated temperature dependent reaction rates of CH2OO and (CH3)2COO with methanol, which have previously been experimentally determined. This methodology is then extended to compute reaction rates of 22 different Criegee intermediates with methanol, including several intermediates derived from isoprene ozonolysis. In some cases, sCI-alcohol reaction rates approach those of sCI-(H2O)2. This suggests that in regions with elevated alcohol concentrations, such as urban Brazil, these reactions may generate significant quantities of AAAHs, and may begin to compete with sCI reactions with other trace tropospheric pollutants such as SO2. This work also demonstrates the ability of alcohols to catalyse the 1,4-H transfer unimolecular decomposition of α-methyl substituted sCIs.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Advanced Research Computing @ Cardiff (ARCCA)
Publisher: American Chemical Society
ISSN: 1089-5639
Funders: EPSRC and EC
Date of First Compliant Deposit: 4 December 2018
Date of Acceptance: 3 December 2018
Last Modified: 23 Nov 2022 10:44

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