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

Abstract: The formation of bimolecular complexes of HOOOH and the HOOO radical with sulfuric acid (H₂SO₄–HOOOH, H₂SO₄–HOOO ) 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 12.7kcalmol⁻¹. This is equivalent to the BE in the H₂SO₄–HOOH complex investigated at the same theoretical level. The complexation of HOOO with H₂SO₄ stabilizes this metastable polyoxide intermediate by about 10.0kcalmol⁻¹. [Copyright &y& Elsevier]