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Comparing electronic structure predictions for the ground state dissociation of vinoxy radicals

J. Chem. Phys. 127, 094309 (2007); doi:10.1063/1.2753489

Published 7 September 2007

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Doran I. G. Bennett and Laurie J. Butler
The James Franck Institute and The Department of Chemistry, The University of Chicago, Chicago, Illinois 60637

Hans-Joachim Werner
Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
This paper reports a series of electronic structure calculations performed on the dissociation pathways of the vinoxy radical (CH2CHO). We use coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)), complete active space self-consistent field (CASSCF), multireference configuration interaction (MRCI), and MRCI with the Davidson correction (MRCI+Q) to calculate the barrier heights of the two unimolecular dissociation pathways of this radical. The effect of state averaging on the barrier heights is investigated at the CASSCF, MRCI, and MRCI+Q levels. The change in mixing angle along the reaction path is calculated as a measure of derivative coupling and found to be insufficient to suggest nonadiabatic recrossing. We also present a new analysis of previous experimental data on the unimolecular dissociation of ground state vinoxy. In particular, an error in the internal energy distribution of vinoxy radicals reported in a previous paper is corrected and a new analysis of the experimental sensitivity to the onset energy (barrier height) for the isomerization reaction is given. Combining these studies, a final “worst case” analysis of the product branching ratio is given and a statistical model using each of the calculated transition states is found to be unable to correctly reproduce the experimental data. ©2007 American Institute of Physics
History: Received 1 May 2007; accepted 6 June 2007; published 7 September 2007
Permalink: http://link.aip.org/link/?JCPSA6/127/094309/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.30.Cf
    Atom and radical chemical reactions; chain reactions, molecule-molecule reactions
  • 82.30.Lp
    Decomposition chemical reactions (pyrolysis, dissociation, and fragmentation)
  • 82.30.Qt
    Isomerization and rearrangement in chemical reactions
  • 82.20.Db
    Transition state theory and statistical theories of rate constants (chemical kinetics)
  • YEAR: 2007

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PUBLICATION DATA

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