Crossed-beam radical-radical reaction dynamics of O(3P)+C 3H3 →h(2S)+C3H2O

Lee Kyoung Kwon, Mi Ja Nam, Sung Eui Youn, Sun Kyu Joo, Hohjai Lee, Jong Ho Choi

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19 Citations (Scopus)

Abstract

The radical-radical oxidation reaction, O (P3) + C3 H3 (propargyl) →H (S2) + C3 H2 O (propynal), was investigated using vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed-beam configuration, together with ab initio and statistical calculations. The barrierless addition of O (P3) to C3 H3 is calculated to form energy-rich addition complexes on the lowest doublet potential energy surface, which subsequently undergo direct decomposition steps leading to the major reaction products, H+ C3 H2 O (propynal). According to the nascent H-atom Doppler-profile analysis, the average translational energy of the products and the fraction of the average transitional energy to the total available energy were determined to be 5.09±0.36 kcalmol and 0.077, respectively. On the basis of a comparison with statistical prior calculations, the reaction mechanism and the significant internal excitation of the polyatomic propynal product can be rationalized in terms of the formation of highly activated, short-lived addition-complex intermediates and the adiabaticity of the excess available energy along the reaction coordinate.

Original languageEnglish
Article number204320
JournalJournal of Chemical Physics
Volume124
Issue number20
DOIs
Publication statusPublished - 2006 May 28

ASJC Scopus subject areas

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

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