Stabilization of metastable hydrogen trioxide (HOOOH) and the hydrotrioxyl radical (HOOO•) by complexation with sulfuric acid. A theoretical study

The formation of bimolecular complexes of HOOOH and the HOOO center dot radical with sulfuric acid (H2SO4-HOOOH, H2SO4-HOOO center dot) has been investigated by using DFT (B3LYP/6-311++G(3df,3pd)) and CCSD(T)-F12 methods. For the first time the structures and the binding energies (BEs) for the various isomeric hydrogen-bonded complexes have been reported. The results reveal an unusually stable H2SO4-HOOOH eight-membered ring structure with two relatively strong hydrogen bonds, and with a calculated BE (CCSD(T)-F12) of 12.7 kcal mol(-1). This is equivalent to the BE in the H2SO4-HOOH complex investigated at the same theoretical level. The complexation of HOOO center dot with H2SO4 stabilizes this metastable polyoxide intermediate by about 10.0 kcal mol(-1). (C) 2013 Elsevier B.V. All rights reserved.