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Gonzalez J, Torrent-Sucarrat M, Anglada JM: The reactions of SO3 with HO2 radical and H2O..HO2 radical complex. Phys Chem Chem Phys. 2010 Mar 7;12(9):2116-25. Epub 2010 Jan 14.
Theoretical study on the atmospheric formation of HSO5 and H2SO4.. The influence of a single water molecule on the gas-phase reactivity of the HO (2) radical has been investigated by studying the reactions of SO (3) with the HO (2) radical and with the H (2) O...HO (2) radical complex. The naked reaction leads to the formation of the HSO (5) radical, with a computed binding energy of 13.81 kcal mol (-1). The reaction with the H (2) O...HO (2) radical complex can give two different products, namely (a) HSO (5) + H (2) O, which has a binding energy that is computed to be 4.76 kcal mol (-1) more stable than the SO (3) + H (2) O...HO (2) reactants (Delta (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 (Delta (E + ZPE) at 0K), with an estimated branching ratio of about 66% at 298K. The fact that one of the products is H (2) SO (4) 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 HO (2), HSO (5), the HSO (5)...H (2) O hydrogen bonded complex, H (2) SO (4), and two H (2) SO (4)...H (2) O complexes, in order to help with the possible experimental identification of some of these species. |
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