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dc.contributor.authorKopp, Wassja A.
dc.contributor.authorKröger, Leif C.
dc.contributor.authorDöntgen, Malte
dc.contributor.authorJacobs, Sascha
dc.contributor.authorBurke, Ultan
dc.contributor.authorCurran, Henry J.
dc.contributor.authorHeufer, Karl Alexander
dc.contributor.authorLeonhard, Kai
dc.date.accessioned2019-01-11T09:15:01Z
dc.date.issued2017-09-06
dc.identifier.citationKopp, Wassja A., Kröger, Leif C., Döntgen, Malte, Jacobs, Sascha, Burke, Ultan, Curran, Henry J., Heufer, Karl Alexander, Leonhard, Kai. (2018). Detailed kinetic modeling of dimethoxymethane. Part I: Ab initio thermochemistry and kinetics predictions for key reactions. Combustion and Flame, 189, 433-442. doi: 10.1016/j.combustflame.2017.07.037en_IE
dc.identifier.issn1556-2921
dc.identifier.urihttp://hdl.handle.net/10379/14788
dc.description.abstractDespite the great interest in oxygenated methyl ethers as diesel fuel additives and as fuels themselves, the influence of their methylenedioxy group(s) (0-CH2-0) has never been quantified using ab initio methods. In this study we elucidate the kinetics and thermochemistry of dimethoxymethane using high-level ab initio (CCSD(T)/aug-cc-pV(D+T)MB2PLYPD3BJ/6-311++g(d,p)) and statistical mechanics methods. We model torsional modes as hindered rotors which has a large influence on the description of the thermal behavior. Rate constants for hydrogen abstraction by H and CH3 are computed and show that abstraction from the methylenedioxy group is favored over abstraction from the terminal methyl groups. beta-scission and isomerization of the radicals are computed using master equations. The effect of rovibrationally excited radicals from preceding hydrogen abstraction reactions on subsequent hot beta-scission is computed and has large influence on the decomposition of the formed dimethylether radical. The quantification of the effect of the dominant methylenedioxy group using ab initio methods can guide modeling of oxygenated methyl ethers that contain that group several times. (C) 2017 The Combustion institute. Published by Elsevier Inc. All rights reserved.en_IE
dc.description.sponsorshipThis work was performed as part of the Cluster of Excellence “Tailor-Made Fuels from Biomass” (EXC 236), which is funded by the Excellence Initiative by the German federal and state governments to promote science and research at German universities. We gratefully acknowledge CPU time grant rwth0070 of the RWTH Aachen University Compute Cluster. M.D. is thankful for financial support from the Deutsche Forschungsgemeinschaft (German Research Association) through grant GSC 111.en_IE
dc.formatapplication/pdfen_IE
dc.language.isoenen_IE
dc.publisherElsevieren_IE
dc.relation.ispartofCombustion And Flameen
dc.subjectOME1en_IE
dc.subjectMethylalen_IE
dc.subjectThermochemistryen_IE
dc.subjectHot beta-scissionen_IE
dc.subjectPOLY(OXYMETHYLENE) DIMETHYL ETHERSen_IE
dc.subjectDENSITY-FUNCTIONAL THEORYen_IE
dc.subjectLOW-TEMPERATURE OXIDATIONen_IE
dc.subjectHYDROGEN ABSTRACTIONen_IE
dc.subjectMASTER EQUATIONen_IE
dc.subjectTHERMODYNAMIC PROPERTIESen_IE
dc.subjectOXYGENATED FUELSen_IE
dc.subjectHEAT-CAPACITYen_IE
dc.subjectN-ALKANESen_IE
dc.subjectCOMBUSTIONen_IE
dc.titleDetailed kinetic modeling of dimethoxymethane. Part I: Ab initio thermochemistry and kinetics predictions for key reactionsen_IE
dc.typeArticleen_IE
dc.date.updated2019-01-08T11:02:06Z
dc.identifier.doi10.1016/j.combustflame.2017.07.037
dc.local.publishedsourcehttps://doi.org/10.1016/j.combustflame.2017.07.037en_IE
dc.description.peer-reviewedpeer-reviewed
dc.contributor.funderDeutsche Forschungsgemeinschaft (German Research Association)en_IE
dc.description.embargo2019-09-06
dc.internal.rssid14062836
dc.local.contactHenry Curran, Dept Of Chemistry, Room 215, Arts/Science Building, Nui Galway. 3856 Email: henry.curran@nuigalway.ie
dc.local.copyrightcheckedYes
dc.local.versionSUBMITTED
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