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

Abstract

The photodissociation of allyl iodide (C{sub 3}H{sub 5}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 C{sub 3}H{sup 3+}. The experimental results are consistent with the earlier results of Szpunar et al. [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*({sup 2}P{sub 1/2}) is more important than previously suspected.

Authors:
; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
939881
Report Number(s):
ANL/CHM/JA-57078
Journal ID: ISSN 0021-9606; JCPSA6; TRN: US200823%%436
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Chem. Phys.; Journal Volume: 124; Journal Issue: 2006
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALLYL RADICALS; STABILITY; PHOTOLYSIS; IODINE COMPOUNDS; DISSOCIATION; CHEMICAL BONDS; CLEAVAGE; ROTATIONAL STATES; VIBRATIONAL STATES; CHEMICAL REACTION KINETICS

Citation Formats

Fan, H., Pratt, S. T., and Chemistry. The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm.. United States: N. p., 2006. Web. doi:10.1063/1.2352733.
Fan, H., Pratt, S. T., & Chemistry. The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm.. United States. doi:10.1063/1.2352733.
Fan, H., Pratt, S. T., and Chemistry. Sun . "The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm.". United States. doi:10.1063/1.2352733.
@article{osti_939881,
title = {The stability of allyl radicals following the photodissociation of allyl iodide at 193 nm.},
author = {Fan, H. and Pratt, S. T. and Chemistry},
abstractNote = {The photodissociation of allyl iodide (C{sub 3}H{sub 5}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 C{sub 3}H{sup 3+}. The experimental results are consistent with the earlier results of Szpunar et al. [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*({sup 2}P{sub 1/2}) is more important than previously suspected.},
doi = {10.1063/1.2352733},
journal = {J. Chem. Phys.},
number = 2006,
volume = 124,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2006},
month = {Sun Jan 01 00:00:00 EST 2006}
}