A combined crossed-beam and ab initio study of the atom-radical reaction dynamics of O(3P) + C2H5→ C2H4 + OH: Analysis of nascent internal state distributions of the OH product

Yong Pal Park, Kyoo Weon Kang, Se Hee Jung, Jong Ho Choi

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Abstract

The oxidation reaction dynamics of ethyl radicals (C2H5) in the gas phase are investigated by applying a combination of high-resolution laser induced fluorescence spectroscopy in a crossed-beam configuration and ab initio theoretical calculations. The supersonic atomic oxygen (O(3P)) and ethyl (C2H5) reactants are produced by photodissociation of NO2 and supersonic flash pyrolysis of a synthesized precursor (azoethane), respectively. An exothermic channel leading to the C2H5 + OH (X2Π: υ″ = 0, 1) products is identified. The nascent rovibrational state distributions of the OH product show substantial bimodal internal excitations consisting of low- and high-N″ components with neither spin-orbit nor Λ-doublet propensities in the ground and first excited vibrational states. The averaged vibrational population (Pυ″), partitioning with respect to the low-N″ components of the υ″ = 0 level, shows a comparable population ratio of P0: P1 = 1: 1.06. On the basis of comparison between the population analyses using ab initio and prior statistical calculations, the title atom-radical reactive scattering processes are governed by dynamic characteristics. The reaction mechanism can be rationalized by two competing mechanisms: abstraction versus addition. The major low N″-components can be described in terms of the direct abstraction process responsible for the comparable vibrational populations, while the minor but hot rotational distribution of the high N″-components implies that some fraction of radical reactants is sampled to proceed through the short-lived addition-complex forming process.

Original languageEnglish
Pages (from-to)7098-7107
Number of pages10
JournalPhysical Chemistry Chemical Physics
Volume12
Issue number26
DOIs
Publication statusPublished - 2010 Jan 1

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ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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