Abstract
Ab initio quantum-chemical calculations of the (CF3CO2H +2 …3O2) and (CF3CO −2 …3O2) complexes were performed by the MP2 method. It was found that these complexes were characterized by low complex formation energies, of 2.97 and 1.72 kcal/mol, respectively. According to the MP2(full)/6-311++G(d, p) calculation data, the bridge stabilization of oxygen by linking with both the CF3CO2H +2 cation and CF3CO −2 anion is much more favorable energetically. A study of the potential energy surface of the joint molecular system (CF3CO2H +2 …3O2…CF3CO −2 ) shows that proton experiences activationless transfer from the cation to the 3O2 molecule accompanied by electron transfer from the CF3COO− anion. An analysis of spin density distribution shows that two radicals are stabilized in the (CF3CO2….OOH….O=C(OH)CF3) complex in the triplet state observed on the potential energy surface.
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Original Russian Text © V.N. Solkan, G.M. Zhidomirov, M.Ya. Mel’nikov, 2010, published in Khimicheskaya Fizika, 2010, Vol. 29, No. 10, pp. 14–17.
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Solkan, V.N., Zhidomirov, G.M. & Mel’nikov, M.Y. The mechanism of formation of the hydroperoxyl radical in the CF3COOH + 3O2 system: a quantum-chemical study. Russ. J. Phys. Chem. B 4, 705–708 (2010). https://doi.org/10.1134/S1990793110050027
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DOI: https://doi.org/10.1134/S1990793110050027