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dc.contributor.authorBugler, John
dc.contributor.authorPower, Jennifer
dc.contributor.authorCurran, Henry J.
dc.date.accessioned2017-07-04T14:08:16Z
dc.date.issued2016-06-09
dc.identifier.citationBugler, John, Power, Jennifer, & Curran, Henry J. (2017). A theoretical study of cyclic ether formation reactions. Proceedings of the Combustion Institute, 36(1), 161-167. doi: https://doi.org/10.1016/j.proci.2016.05.006en_IE
dc.identifier.issn1540-7489
dc.identifier.urihttp://hdl.handle.net/10379/6649
dc.description.abstractCyclisation reactions of hydroperoxyl-alkyl radicals forming cyclic ethers and hydroxyl radicals play an important role in low temperature oxidation chemistry. These reactions contribute to the competition be-tween radical chain propagation and chain branching reaction pathways which dominate the reactivity of alkanes at temperatures where negative temperature coefficient (NTC) behaviour is often observed. This work is motivated by previous experimental and modelling evidences that current literature rate coefficients for these reactions are in need of refinement and/or re-determination. In light of this, the current study presents quantum-chemically-derived high-pressure limit rate coefficients for all cyclisation reactions leading to cyclic ether formation in alkanes ranging in size from C-2 to C-5. Ro-vibrational properties of each stationary point were determined at the M06-2X/6-311 ++ G(d, p) level of theory. Coupled cluster (CCSD(T)) and Moller-Plesset perturbation theory (MP2) methods were employed with various basis sets and complete basis set extrapolation techniques to compute the energies of the resulting geometries. These methods, combined with canonical transition state theory, have been used to determine 43 rate coefficients, with enough structural diversity within the reactions to allow for their application to larger species for which the use of the levels of theory employed herein would be computationally prohibitive. The validity of an alternative, and com-putationally less expensive, technique to approximate the complete basis set limit energies is also discussed, together with implications of this work for combustion modelling. (C) 2016 by The Combustion Institute. Published by Elsevier Inc.en_IE
dc.description.sponsorshipThe authors wish to acknowledge the support of the Irish Research Council in funding this project under project number EPSPG/2012/380, and also the provision of computational resources from the Irish Centre for High-End Computing, ICHEC, under project number ngche026c.en_IE
dc.formatapplication/pdfen_IE
dc.language.isoenen_IE
dc.publisherElsevieren_IE
dc.relation.ispartofProceedings Of The Combustion Instituteen
dc.subjectKineticsen_IE
dc.subjectAb initioen_IE
dc.subjectRate coefficienten_IE
dc.subjectCyclic etheren_IE
dc.subjectHydroperoxyl-alkyl radicalen_IE
dc.subjectCompound methods CBS-QB3en_IE
dc.subjectActive thermochemical tablesen_IE
dc.subjectSet model chemistryen_IE
dc.subjectPressure rate rulesen_IE
dc.subjectFormation enthalpiesen_IE
dc.subjectMolecular energiesen_IE
dc.subjectCBS-APNOen_IE
dc.subjectGAUSSIAN-1 theoryen_IE
dc.subject2nd-row compoundsen_IE
dc.subjectProduct formationen_IE
dc.titleA theoretical study of cyclic ether formation reactionsen_IE
dc.typeArticleen_IE
dc.date.updated2017-07-03T16:16:20Z
dc.identifier.doi10.1016/j.proci.2016.05.006
dc.local.publishedsourcehttps://doi.org/10.1016/j.proci.2016.05.006en_IE
dc.description.peer-reviewedpeer-reviewed
dc.contributor.funder|~|
dc.description.embargo2018-06-09
dc.internal.rssid12329176
dc.local.contactHenry Curran, Dept Of Chemistry, Room 215, Arts/Science Building, Nui Galway. 3856 Email: henry.curran@nuigalway.ie
dc.local.copyrightcheckedNo
dc.local.versionACCEPTED
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