Energetics and mechanisms for the acetonyl radical + O2 reaction: An important system for atmospheric and combustion chemistry

Weidman, Jared D.; Turney, Justin M.; Schaefer, Henry F.

doi:10.1063/1.5141859

Title: Energetics and mechanisms for the acetonyl radical + O₂ reaction: An important system for atmospheric and combustion chemistry

Journal Article · Sat Mar 21 00:00:00 EDT 2020 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5141859· OSTI ID:1803414

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Univ. of Georgia, Athens, GA (United States). Center for Computational Quantum Chemistry

The acetonyl radical (•CH₂COCH₃) is relevant to atmospheric and combustion chemistry due to its prevalence in many important reaction mechanisms. One such reaction mechanism is the decomposition of Criegee intermediates in the atmosphere that can produce acetonyl radical and OH. In order to understand the fate of the acetonyl radical in these environments and to create more accurate kinetics models, we have examined the reaction system of the acetonyl radical with O₂ using highly reliable theoretical methods. Structures were optimized using coupled cluster theory with singles, doubles, and perturbative triples [CCSD(T)] with an atomic natural orbital (ANO0) basis set. Energetics were computed to chemical accuracy using the focal point approach involving perturbative treatment of quadruple excitations [CCSDT(Q)] and basis sets as large as cc-pV5Z. The addition of O₂ to the acetonyl radical produces the acetonylperoxy radical, and multireference computations on this reaction suggest it to be barrierless. Additionally, no submerged pathways were found for the unimolecular isomerization of the acetonylperoxy radical. Besides dissociation to reactants, the lowest energy pathway available for the acetonylperoxy radical is a 1-5 H shift from the methyl group to the peroxy group through a transition state that is 3.3 kcal mol^-1 higher in energy than acetonyl radical + O₂. The ultimate products from this pathway are the enol tautomer of the acetonyl radical along with O₂. Multiple pathways that lead to OH formation are considered; however, all of these pathways are predicted to be energetically inaccessible, except at high temperatures.

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Research Organization:: Univ. of Georgia, Athens, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018412

OSTI ID:: 1803414

Alternate ID(s):: OSTI ID: 1605622

Journal Information:: Journal of Chemical Physics, Vol. 152, Issue 11; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 3 works

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Title: Energetics and mechanisms for the acetonyl radical + O2 reaction: An important system for atmospheric and combustion chemistry

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