Photofragmentation of mono- and dichloroethylenes: Translational energy measurements of recoiling Cl and HCl fragments

Article abstract of DOI:10.1063/1.449403

Translational energy (E_t) spectra of Cl and HCl fragments from vinylchloride, trans- dichloroethylene, cis-dichloroethylene, and 1,1'-dichloroethylene have been measured for the ?*<-? excitation at 193 nm.E_t distribution and angular dependence of the Cl fragment indicate that the two-center dissociation occurs in a time faster than a rotation period and the recoiling organic radical (the counter fragment) is highly vibrationally excited.In dichloroethylenes, the presence of a second channel producing Cl atoms has been confirmed and attributed to the dissociation from the lower (n,?*) state through a (?,?*) state.The E_t distribution of HCl fragments is nonstatistical and found to converge to null population at an energy less than half of the total available energy.This convergence point coincides with the value of the local available energy for the elimination reaction (activation energy -ΔH_reaction⁰).The yield of HCl molecules relative to Cl atoms is estimated to be ca. 1.1 for vinylchloride.High efficiency of the HCl elimination is attributed to a rapid internal conversion from the (?,?*) state to the lowest (?,?*) state from which the pathway to the transition state for HCl elimination is opened in ground electronic manifolds.

Full text of DOI:10.1063/1.449403

Photofragmentation of mono and dichloroethylenes: Translational energy
measurements of recoiling Cl and HCl fragments
Masayuki Umemoto, Kanekazu Seki, Hisanori Shinohara, Umpei Nagashima, Nobuyuki Nishi, Minoru
Kinoshita, and Ryoichi Shimada
Citation: The Journal of Chemical Physics 83, 1657 (1985); doi: 10.1063/1.449403
View online: http://dx.doi.org/10.1063/1.449403
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/83/4?ver=pdfcov
Published by the AIP Publishing
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
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This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
132.174.255.116 On: Mon, 22 Dec 2014 03:50:32

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
132.174.255.116 On: Mon, 22 Dec 2014 03:50:32

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
132.174.255.116 On: Mon, 22 Dec 2014 03:50:32

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
132.174.255.116 On: Mon, 22 Dec 2014 03:50:32

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
132.174.255.116 On: Mon, 22 Dec 2014 03:50:32

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
132.174.255.116 On: Mon, 22 Dec 2014 03:50:32

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
132.174.255.116 On: Mon, 22 Dec 2014 03:50:32

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
132.174.255.116 On: Mon, 22 Dec 2014 03:50:32