A combined crossed-beam and theoretical study of the reaction dynamics of O(3P) C2H3 → C2H2 OH: Analysis of the nascent OH products with the preferential population of the Π(A′) component

Min Jin Park, Su Chan Jang, Jong Ho Choi

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3 Citations (Scopus)

Abstract

The gas-phase reaction dynamics of ground-state atomic oxygen O( 3P) 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 J. Phys. Chem. Ref. Data 34, 757 (2005)10.1063/1.1748524, a new exothermic channel of O(3P) C 2H3 → C2H2 OH (X 2Π: υ″ 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 Π(A )Π(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 Π(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.

Original languageEnglish
Article number204311
JournalJournal of Chemical Physics
Volume137
Issue number20
DOIs
Publication statusPublished - 2012 Nov 28

ASJC Scopus subject areas

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

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