High-level theoretical characterization of the vinoxy radical (•CH2CHO) + O2 reaction
Abstract
Numerous processes in atmospheric and combustion chemistry produce the vinoxy radical (•CH2CHO). To understand the fate of this radical and to provide reliable energies needed for kinetic modeling of such processes, we have examined its reaction with O2 using highly reliable theoretical methods. Utilizing the focal point approach, the energetics of this reaction and subsequent reactions were obtained using coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] extrapolated to the complete basis set limit. These extrapolated energies were appended with several corrections including a treatment of full triples and connected quadruple excitations, i.e., CCSDT(Q). In addition, this study models the initial vinoxy radical + O2 reaction for the first time with multireference methods. We predict a barrier for this reaction of approximately 0.4 kcal mol–1. This result agrees with experimental findings but is in disagreement with previous theoretical studies. The vinoxy radical + O2 reaction produces a 2-oxoethylperoxy radical which can undergo a number of unimolecular reactions. Abstraction of a β-hydrogen (a 1,4-hydrogen shift) and dissociation back to reactants are predicted to be competitive to each other due to their similar barriers of 21.2 and 22.3 kcal mol–1, respectively. The minimum-energy β-hydrogen abstraction pathway produces a hydroperoxy radicalmore »
- Authors:
-
- Univ. of Georgia, Athens, GA (United States)
- Publication Date:
- Research Org.:
- Univ. of Georgia, Athens, GA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1468300
- Grant/Contract Number:
- SC0018412
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 148; Journal Issue: 18; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Weidman, Jared D., Allen, Ryan T., Moore, III, Kevin B., and Schaefer, III, Henry F. High-level theoretical characterization of the vinoxy radical (•CH2CHO) + O2 reaction. United States: N. p., 2018.
Web. doi:10.1063/1.5026295.
Weidman, Jared D., Allen, Ryan T., Moore, III, Kevin B., & Schaefer, III, Henry F. High-level theoretical characterization of the vinoxy radical (•CH2CHO) + O2 reaction. United States. https://doi.org/10.1063/1.5026295
Weidman, Jared D., Allen, Ryan T., Moore, III, Kevin B., and Schaefer, III, Henry F. Mon .
"High-level theoretical characterization of the vinoxy radical (•CH2CHO) + O2 reaction". United States. https://doi.org/10.1063/1.5026295. https://www.osti.gov/servlets/purl/1468300.
@article{osti_1468300,
title = {High-level theoretical characterization of the vinoxy radical (•CH2CHO) + O2 reaction},
author = {Weidman, Jared D. and Allen, Ryan T. and Moore, III, Kevin B. and Schaefer, III, Henry F.},
abstractNote = {Numerous processes in atmospheric and combustion chemistry produce the vinoxy radical (•CH2CHO). To understand the fate of this radical and to provide reliable energies needed for kinetic modeling of such processes, we have examined its reaction with O2 using highly reliable theoretical methods. Utilizing the focal point approach, the energetics of this reaction and subsequent reactions were obtained using coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)] extrapolated to the complete basis set limit. These extrapolated energies were appended with several corrections including a treatment of full triples and connected quadruple excitations, i.e., CCSDT(Q). In addition, this study models the initial vinoxy radical + O2 reaction for the first time with multireference methods. We predict a barrier for this reaction of approximately 0.4 kcal mol–1. This result agrees with experimental findings but is in disagreement with previous theoretical studies. The vinoxy radical + O2 reaction produces a 2-oxoethylperoxy radical which can undergo a number of unimolecular reactions. Abstraction of a β-hydrogen (a 1,4-hydrogen shift) and dissociation back to reactants are predicted to be competitive to each other due to their similar barriers of 21.2 and 22.3 kcal mol–1, respectively. The minimum-energy β-hydrogen abstraction pathway produces a hydroperoxy radical (QOOH) that eventually decomposes to formaldehyde, CO, and •OH. Two other unimolecular reactions of the peroxy radical are α-hydrogen abstraction (38.7 kcal mol–1 barrier) and HO2• elimination (43.5 kcal mol–1 barrier). Furthermore, these pathways lead to glyoxal + •OH and ketene + HO2• formation, respectively, but they are expected to be uncompetitive due to their high barriers.},
doi = {10.1063/1.5026295},
journal = {Journal of Chemical Physics},
number = 18,
volume = 148,
place = {United States},
year = {Mon May 14 00:00:00 EDT 2018},
month = {Mon May 14 00:00:00 EDT 2018}
}
Web of Science
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Characterization of the 2-methylvinoxy radical + O 2 reaction: A focal point analysis and composite multireference study
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