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J Chem Phys. 2007 Sep 7;127(9):094309.

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

Author information

1
The James Franck Institute and The Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, USA.

Abstract

This paper reports a series of electronic structure calculations performed on the dissociation pathways of the vinoxy radical (CH(2)CHO). 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.

PMID:
17824741
DOI:
10.1063/1.2753489

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