A combined crossed-beam and theoretical study of the reaction dynamics of O(P-3)+C2H3 -> C2H2+OH: Analysis of the nascent OH products with the preferential population of the Pi(A ') component
DC Field | Value | Language |
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dc.contributor.author | Park, Min-Jin | - |
dc.contributor.author | Jang, Su-Chan | - |
dc.contributor.author | Choi, Jong-Ho | - |
dc.date.accessioned | 2021-09-06T12:57:25Z | - |
dc.date.available | 2021-09-06T12:57:25Z | - |
dc.date.created | 2021-06-14 | - |
dc.date.issued | 2012-11-28 | - |
dc.identifier.issn | 0021-9606 | - |
dc.identifier.uri | https://scholar.korea.ac.kr/handle/2021.sw.korea/106913 | - |
dc.description.abstract | The gas-phase reaction dynamics of ground-state atomic oxygen [O(P-3) from the photo-dissociation of NO2] with vinyl radicals [C2H3 from the supersonic flash pyrolysis of vinyl iodide, C2H3I] has been investigated using a combination of high-resolution laser-induced fluorescence spectroscopy in a crossed-beam configuration and ab initio calculations. Unlike the previous gas-phase bulk kinetic experiments by Baulch et al. [J. Phys. Chem. Ref. Data 34, 757 (2005)], a new exothermic channel of O(P-3) + C2H3 -> C2H2 + OH (X (2)Pi: upsilon '' = 0) has been identified for the first time, and the population analysis shows bimodal nascent rotational distributions of OH products with low-and high-N '' components with a ratio of 2.4:1. No spin-orbit propensities were observed, and the averaged ratios of Pi(A')/Pi(A '') were determined to be 1.66 +/- 0.27. On the basis of computations at the CBS-QB3 theory level and comparison with prior theory, the microscopic mechanisms responsible for the nascent populations can be understood in terms of two competing dynamical pathways: a direct abstraction process in the low-N '' regime as the major pathway and an addition-complex forming process in the high-N '' regime as the minor pathway. Particularly, during the bond cleavage process of the weakly bound van der Waals complex C2H2-OH, the characteristic pathway from the low dihedral-angle geometry was consistent with the observed preferential population of the Pi(A') component in the nascent OH products. A molecular-level discussion of the reactivity, mechanism, and dynamical features of the title reaction are presented together with a comparison to gas-phase oxidation reactions of a series of prototypical hydrocarbon radicals. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4767772] | - |
dc.language | English | - |
dc.language.iso | en | - |
dc.publisher | AMER INST PHYSICS | - |
dc.subject | RADICAL-RADICAL REACTION | - |
dc.subject | EVALUATED KINETIC-DATA | - |
dc.subject | A-X SYSTEM | - |
dc.subject | CHEMICAL-DYNAMICS | - |
dc.subject | O(P-3(J))+HYDROCARBON REACTIONS | - |
dc.subject | SATURATED-HYDROCARBONS | - |
dc.subject | LASER PHOTOLYSIS | - |
dc.subject | O(P-3) | - |
dc.subject | ENERGY | - |
dc.subject | C3H8 | - |
dc.title | A combined crossed-beam and theoretical study of the reaction dynamics of O(P-3)+C2H3 -> C2H2+OH: Analysis of the nascent OH products with the preferential population of the Pi(A ') component | - |
dc.type | Article | - |
dc.contributor.affiliatedAuthor | Choi, Jong-Ho | - |
dc.identifier.doi | 10.1063/1.4767772 | - |
dc.identifier.scopusid | 2-s2.0-84870554402 | - |
dc.identifier.wosid | 000312252100036 | - |
dc.identifier.bibliographicCitation | JOURNAL OF CHEMICAL PHYSICS, v.137, no.20 | - |
dc.relation.isPartOf | JOURNAL OF CHEMICAL PHYSICS | - |
dc.citation.title | JOURNAL OF CHEMICAL PHYSICS | - |
dc.citation.volume | 137 | - |
dc.citation.number | 20 | - |
dc.type.rims | ART | - |
dc.type.docType | Article | - |
dc.description.journalClass | 1 | - |
dc.description.journalRegisteredClass | scie | - |
dc.description.journalRegisteredClass | scopus | - |
dc.relation.journalResearchArea | Chemistry | - |
dc.relation.journalResearchArea | Physics | - |
dc.relation.journalWebOfScienceCategory | Chemistry, Physical | - |
dc.relation.journalWebOfScienceCategory | Physics, Atomic, Molecular & Chemical | - |
dc.subject.keywordPlus | RADICAL-RADICAL REACTION | - |
dc.subject.keywordPlus | EVALUATED KINETIC-DATA | - |
dc.subject.keywordPlus | A-X SYSTEM | - |
dc.subject.keywordPlus | CHEMICAL-DYNAMICS | - |
dc.subject.keywordPlus | O(P-3(J))+HYDROCARBON REACTIONS | - |
dc.subject.keywordPlus | SATURATED-HYDROCARBONS | - |
dc.subject.keywordPlus | LASER PHOTOLYSIS | - |
dc.subject.keywordPlus | O(P-3) | - |
dc.subject.keywordPlus | ENERGY | - |
dc.subject.keywordPlus | C3H8 | - |
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