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Photofragment imaging study of the CH2CCH2OH radical intermediate of the OH+allene reaction

J. Chem. Phys. 127, 154316 (2007); doi:10.1063/1.2776268

Published 18 October 2007

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Arjun S. Raman, M. Justine Bell, Kai-Chung Lau, and Laurie J. Butler
The James Franck Institute and Department of Chemistry, University of Chicago, Chicago, Illinois 60637, USA
These velocity map imaging experiments characterize the photolytic generation of one of the two radical intermediates formed when OH reacts via an addition mechanism with allene. The CH2CCH2OH radical intermediate is generated photolytically from the photodissociation of 2-chloro-2-propen-1-ol at 193  nm. Detecting the Cl atoms using [2+1] resonance-enhanced multiphoton ionization evidences an isotropic angular distribution for the Cl+CH2CCH2OH photofragments, a spin-orbit branching ratio for Cl(2P1/2):Cl(2P3/2) of 0.28, and a bimodal recoil kinetic energy distribution. Conservation of momentum and energy allows us to determine from this data the internal energy distribution of the nascent CH2CCH2OH radical cofragment. To assess the possible subsequent decomposition pathways of this highly vibrationally excited radical intermediate, we include electronic structure calculations at the G3//B3LYP level of theory. They predict the isomerization and dissociation transition states en route from the initial CH2CCH2OH radical intermediate to the three most important product channels for the OH+allene reaction expected from this radical intermediate: formaldehyde+C2H3, H+acrolein, and ethene+CHO. We also calculate the intermediates and transition states en route from the other radical adduct, formed by addition of the OH to the center carbon of allene, to the ketene+CH3 product channel. We compare our results to a previous theoretical study of the O+allyl reaction conducted at the CBS-QB3 level of theory, as the two reactions include several common intermediates. ©2007 American Institute of Physics
History: Received 18 June 2007; accepted 2 August 2007; published 18 October 2007
Permalink: http://link.aip.org/link/?JCPSA6/127/154316/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.50.Hp
    Chemical processes caused by visible and UV light
  • 82.30.Cf
    Atom and radical chemical reactions; chain reactions, molecule-molecule reactions
  • 82.30.Nr
    Association, addition, insertion, cluster formation (chemical reactions)
  • 82.30.Qt
    Isomerization and rearrangement in chemical reactions
  • 82.20.Hf
    Product distribution in chemical kinetics
  • 82.20.Rp
    State to state energy transfer in chemical reactions
  • YEAR: 2007

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (35)
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