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

Research output: Contribution to journalArticle

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

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Ultraviolet lasers
Potential energy surfaces
Fluorescence spectroscopy
Reaction products
Vacuum
Decomposition
Atoms
Oxidation
energy
products
ultraviolet lasers
reaction products
laser induced fluorescence
potential energy
decomposition
vacuum
oxidation
profiles
configurations
spectroscopy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Crossed-beam radical-radical reaction dynamics of O(3P)+C 3H3 →h(2S)+C3H2O. / Kwon, Lee Kyoung; Nam, Mi Ja; Youn, Sung Eui; Joo, Sun Kyu; Lee, Hohjai; Choi, Jong-Ho.

In: Journal of Chemical Physics, Vol. 124, No. 20, 204320, 28.05.2006.

Research output: Contribution to journalArticle

Kwon, Lee Kyoung ; Nam, Mi Ja ; Youn, Sung Eui ; Joo, Sun Kyu ; Lee, Hohjai ; Choi, Jong-Ho. / Crossed-beam radical-radical reaction dynamics of O(3P)+C 3H3 →h(2S)+C3H2O. In: Journal of Chemical Physics. 2006 ; Vol. 124, No. 20.
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