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Issue 9, 2010
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The reactions of SO3 with HO2 radical and H2O⋯HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4

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Abstract

The influence of a single water molecule on the gas-phase reactivity of the HO2 radical has been investigated by studying the reactions of SO3 with the HO2 radical and with the H2O⋯HO2 radical complex. The naked reaction leads to the formation of the HSO5 radical, with a computed binding energy of 13.81 kcal mol−1. The reaction with the H2O⋯HO2 radical complex can give two different products, namely (a) HSO5 + H2O, which has a binding energy that is computed to be 4.76 kcal mol−1 more stable than the SO3 + H2O⋯HO2 reactants (Δ(E + ZPE) at 0K) and an estimated branching ratio of about 34% at 298K and (b) sulfuric acid and the hydroperoxyl radical, which is computed to be 10.51 kcal mol−1 below the energy of the reactants (Δ(E + ZPE) at 0K), with an estimated branching ratio of about 66% at 298K. The fact that one of the products is H2SO4 may have relevance in the chemistry of the atmosphere. Interestingly, the water molecule acts as a catalyst, [as it occurs in (a)] or as a reactant [as it occurs in (b)]. For a sake of completeness we have also calculated the anharmonic vibrational frequencies for HO2, HSO5, the HSO5⋯H2O hydrogen bonded complex, H2SO4, and two H2SO4⋯H2O complexes, in order to help with the possible experimental identification of some of these species.

Graphical abstract: The reactions of SO3 with HO2 radical and H2O⋯HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4

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Publication details

The article was received on 12 Aug 2009, accepted on 09 Dec 2009 and first published on 14 Jan 2010


Article type: Paper
DOI: 10.1039/B916659A
Citation: Phys. Chem. Chem. Phys., 2010,12, 2116-2125

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    The reactions of SO3 with HO2 radical and H2O⋯HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4

    J. Gonzalez, M. Torrent-Sucarrat and J. M. Anglada, Phys. Chem. Chem. Phys., 2010, 12, 2116
    DOI: 10.1039/B916659A

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