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dc.contributor.authorXing, Lili
dc.contributor.authorBao, Junwei Lucas
dc.contributor.authorWang, Zhandong
dc.contributor.authorWang, Xuetao
dc.contributor.authorTruhlar, Donald G.
dc.date.accessioned2018-10-07T06:56:46Z
dc.date.available2018-10-07T06:56:46Z
dc.date.issued2018-08-08
dc.identifier.citationXing L, Bao JL, Wang Z, Wang X, Truhlar DG (2018) Hydrogen shift isomerizations in the kinetics of the second oxidation mechanism of alkane combustion. Reactions of the hydroperoxypentylperoxy OOQOOH radical. Combustion and Flame 197: 88–101. Available: http://dx.doi.org/10.1016/j.combustflame.2018.07.013.
dc.identifier.issn0010-2180
dc.identifier.doi10.1016/j.combustflame.2018.07.013
dc.identifier.urihttp://hdl.handle.net/10754/628878
dc.description.abstractHydroperoxyalkylperoxy species are important intermediates that are generated during the autoignition of transport fuels. In combustion, the fate of hydroperoxyalkylperoxy is important for the performance of advanced combustion engines, especially for autoignition. A key fate of the hydroperoxyalkylperoxy is a 1,5 H-shift, for which kinetics data are experimentally unavailable. In the present work, we study 1-hydroperoxypentan-3-yl)dioxidanyl (CH3CH2CH(OO)CH2CH2OOH) as a model compound to clarify the kinetics of 1,5 H-shift of hydroperoxyalkylperoxy species, in particular α-H isomerization and alternative competitive pathways. With a combination of electronic structure calculations, we determine previously missing thermochemical data, and with multipath variational transition state theory (MP-VTST), a multidimensional tunneling (MT) approximation, multiple-structure anharmonicity, and torsional potential anharmonicity, we obtained much more accurate rate constants than the ones that can computed by conventional single-structure harmonic transition state theory (TST) and than the empirically estimated rate constants that are currently used in combustion modeling. The roles of various factors in determining the rates are elucidated. The pressure-dependent rate constants for these competitive reactions are computed using system-specific quantum RRK theory. The calculated temperature range is 298–1500 K, and the pressure range is 0.01–100 atm. The accurate thermodynamic and kinetics data determined in this work are indispensable in the detailed understanding and prediction of ignition properties of hydrocarbons and alternative fuels.
dc.description.sponsorshipThis work was supported in part by Key Science Foundation of Higher Education of Henan (19A480002), by the U.S. Department of Energy, Office of Basic Energy Sciences, under Award Number DE-SC0015997, by King Abdullah University of Science and Technology (KAUST), Office of Sponsored Research (OSR) under Award No. OSR-2016-CRG5-3022 and Saudi Aramco under the FUELCOM program, by the Henan Science and Technology Innovation Talent Program (Outstanding Youth) (114100510010), and by the National Natural Science Foundation of Henan Province (182300410256). The authors are grateful to Feng Zhang for helpful discussions.
dc.publisherElsevier BV
dc.relation.urlhttp://www.sciencedirect.com/science/article/pii/S0010218018303377
dc.rightsNOTICE: this is the author’s version of a work that was accepted for publication in Combustion and Flame. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Combustion and Flame, [, , (2018-08-08)] DOI: 10.1016/j.combustflame.2018.07.013. © 2018. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subjectHydroperoxyalkylperoxy
dc.subjectAutoignition
dc.subjectQuantum chemical calculation
dc.subjectKinetics
dc.titleHydrogen shift isomerizations in the kinetics of the second oxidation mechanism of alkane combustion. Reactions of the hydroperoxypentylperoxy OOQOOH radical
dc.typeArticle
dc.contributor.departmentClean Combustion Research Center
dc.identifier.journalCombustion and Flame
dc.eprint.versionPost-print
dc.contributor.institutionDepartment of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota, MN 55455-0431, USA
dc.contributor.institutionEnergy and Power Engineering Institute, Henan University of Science and Technology, Luoyang, Henan 471003, China
kaust.personWang, Zhandong
kaust.grant.numberOSR-2016-CRG5-3022
refterms.dateFOA2018-10-07T08:21:48Z
dc.date.published-online2018-08-08
dc.date.published-print2018-11


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