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dc.contributor.authorSun, Yanjin
dc.contributor.authorZhou, Chong-Wen
dc.contributor.authorSomers, Kieran P.
dc.contributor.authorCurran, Henry J.
dc.date.accessioned2020-10-12T08:48:31Z
dc.date.issued2020-05-12
dc.identifier.citationSun, Yanjin, Zhou, Chong-Wen, Somers, Kieran P., & Curran, Henry J. (2020). An ab Initio/Transition State Theory Study of the Reactions of Ċ5H9 Species of Relevance to 1,3-Pentadiene, Part II: Pressure Dependent Rate Constants and Implications for Combustion Modeling. The Journal of Physical Chemistry A, 124(23), 4605-4631. doi:10.1021/acs.jpca.0c02244en_IE
dc.identifier.issn1089-5639
dc.identifier.issn1520-5215
dc.identifier.urihttp://hdl.handle.net/10379/16218
dc.description.abstractThe temperature- and pressure-dependence of rate constants for several radicals and unsaturated hydrocarbons reactions (1,3-C5H8/1,4-C5H8/cyC(5)H(8) + (H)over dot, C2H4 + (C)over dot(3)H5-a, C3H6 + (C)over dot(2)H(3)) are analyzed in this paper. The abstraction reactions of these systems are also calculated and compared with available literature data. (C)over dot(5)H(9) radicals can be produced via (H)over dot atom addition reactions to the pentadiene isomers and cyclopentene, and also by H-atom abstraction reactions from 1- and 2-pentene and cyclopentane. Comprehensive (C)over dot(5)H(9) potential energy surface (PES) analyses and high-pressure limiting rate constants for related reactions have been explored in part I of this work (J. Phys. Chem. A 2019, 123 (22), 9019-9052). In this work, a chemical kinetic model is constructed based on the computed thermochemistry and high-pressure limiting rate constants from part I, to further understand the chemistry of different C5H8 molecules. The most important channels for these addition reactions are discussed in the present work based on reaction pathway analyses. The dominant reaction pathways for these five systems are combined together to generate a simplified (C)over dot(5)H(9) PES including nine reactants, 25 transition states (TSs), and nine products. Spin-restricted single point energies are calculated for radicals and TSs on the simplified PES at the ROCCSD(T)/aug-cc-pVTZ level of theory with basis set corrections from MP2/aug-cc-pVXZ (where X = T and Q). Temperature- and pressure-dependent rate constants are calculated using RRKM theory with a Master Equation analysis, with restricted energies used for minima on the simplified (C)over dot(5)H(9) PES and unrestricted energies for other species, over a temperature range of 300-2000 K and in the pressure range 0.01-100 atm. The rate constants calculated are in good agreement with those in the literature. The chemical kinetic model is updated with pressure-dependent rate constants and is used to simulate the species concentration profiles for H. atom addition to cyclopentane and cyclopentene. Through detailed analyses and comparisons, this model can reproduce the experimental measurements of species qualitatively and quantitatively with reasonably good agreement.en_IE
dc.description.sponsorshipThis study is supported by Science Foundation Ireland and the China Scholarship Council (CSC). The authors want to acknowledge the financial support of Science Foundation Ireland under Grant No. 15/IA/3177 and 16/SP/3829, and the provision of computational resources from ICHEC under the NUI Galway shared condominium accounts. The Computational resources are provided by the Irish Centre for High-End Computing (ICHEC), under project number ngche063c, ngcom006c and ngche058c. The authors are grateful to Stephen Klippenstein for the help with MESS code study. Chong-Wen Zhou acknowledges the support from National Science and Technology Major Project (2017-III-0004-0028) and Beihang University under the Fundamental Research Funds.en_IE
dc.formatapplication/pdfen_IE
dc.language.isoenen_IE
dc.publisherAmerican Chemical Societyen_IE
dc.relation.ispartofJournal Of Physical Chemistry Aen
dc.subjectIGNITION DELAY-TIMEen_IE
dc.subjectMASTER EQUATIONen_IE
dc.subjectMULTIPLE-WELLen_IE
dc.subjectSHOCK-TUBEen_IE
dc.subjectTEMPERATURE-DEPENDENCEen_IE
dc.subjectACTIVATION-ENERGIESen_IE
dc.subjectRADICAL-ADDITIONen_IE
dc.subjectATOM ADDITIONen_IE
dc.subjectDECOMPOSITIONen_IE
dc.subjectCYCLOPENTYLen_IE
dc.titleAn ab initio/transition state theory study of the reactions of Ċ5H9 species of relevance to 1,3-Pentadiene, Part II: Pressure dependent rate constants and implications for combustion modelingen_IE
dc.typeArticleen_IE
dc.date.updated2020-10-09T13:33:36Z
dc.identifier.doi10.1021/acs.jpca.0c02244
dc.local.publishedsourcehttps://doi.org/10.1021/acs.jpca.0c02244en_IE
dc.description.peer-reviewedpeer-reviewed
dc.contributor.funderScience Foundation Irelanden_IE
dc.description.embargo2021-05-12
dc.internal.rssid21750262
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.versionACCEPTED
dcterms.projectinfo:eu-repo/grantAgreement/SFI/SFI Investigator Programme/15/IA/3177/IE/Combustion Chemistry for Sustainable Fuel Utilization/en_IE
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