The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm

H. Fan, S. T. Pratt

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)

Abstract

The photodissociation of allyl iodide (C3 H5 I) at 193 nm was investigated by using a combination of vacuum-ultraviolet photoionization of the allyl radical, resonant multiphoton ionization of the iodine atoms, and velocity map imaging. The data provide insight into the primary C-I bond fission process and into the dissociative ionization of the allyl radical to produce C3 H3+. The experimental results are consistent with the earlier results of Szpunar [J. Chem. Phys. 119, 5078 (2003)], in that some allyl radicals with internal energies higher than the secondary dissociation barrier are found to be stable. This stability results from the partitioning of available energy between the rotational and vibrational degrees of freedom of the radical, the effects of a centrifugal barrier along the reaction coordinate, and the effects of the kinetic shift in the secondary dissociation of the allyl radical. The present results suggest that the primary dissociation of allyl iodide to allyl radicals plus I* (P 12 2) is more important than previously suspected.

Original languageEnglish
Article number144302
JournalJournal of Chemical Physics
Volume125
Issue number14
DOIs
Publication statusPublished - Oct 20 2006

ASJC Scopus subject areas

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

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