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Issue 21, 2001
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Theoretical study on the atmospheric fate of carbonyl radicals: kinetics of decomposition reactions

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Abstract

The decomposition kinetics of a large set of representative R–CO carbonyl radicals has been studied theoretically. These radicals can either decompose into R + CO or, in the presence of oxygen, add to O2 to give acylperoxy radicals RC(O)O2. In this work, it is shown, by comparison to available experimental data, that reliable quantitative kinetic parameters for decomposition reactions can be obtained using DFT (B3LYP and BH&HLYP functionals) and ab initio G2(MP2) methods. Moreover, it has been demonstrated, by performing RRKM calculations, that the dissociation of carbonyl radicals under atmospheric conditions is not only governed by the height of the barriers, but that pressure effects can also play an important role and must be taken into account. Structure–activity relationships for the decomposition of R–CO radicals are presented according to the nature of the R group. The R–CO radicals, which are predicted to decompose under atmospheric conditions, contain chlorine or oxygen in the R group.

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Publication details

The article was received on 02 Jul 2001, accepted on 03 Sep 2001 and first published on 08 Oct 2001


Article type: Paper
DOI: 10.1039/B105824J
Citation: Phys. Chem. Chem. Phys., 2001,3, 4712-4717
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    Theoretical study on the atmospheric fate of carbonyl radicals: kinetics of decomposition reactions

    R. Méreau, M. Rayez, J. Rayez, F. Caralp and R. Lesclaux, Phys. Chem. Chem. Phys., 2001, 3, 4712
    DOI: 10.1039/B105824J

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