Theoretical Study of the HOCH2OO• + HO2 • Reaction: Detailed Molecular Mechanisms of the Three Reaction Channels

Abstract

Abstract The HO2 • + HOCH2OO• reaction was theoretically investigated, using various high-level, single-reference Complete Basis Set methods including CBS-QB3, CBS-QCI/APNO and CBS-Q(MPW1B95) and a new multi-reference CI-PT2 approach. Three major product channels under atmospheric conditions were identified and their molecular mechanisms elucidated in great detail by Intrinsic Reaction Coordinate Analyses (IRC) at the B3LYP/6–311G(d,p) level: (i) Direct head-to-tail H-atom abstraction from the hydroperoxy radical by the alkylperoxy, occurring on the triplet Potential Energy Surface (PES) leading to HOCH2OOH + O2; (ii) A two-step rearrangement of the initial singlet HOCH2OOOOH tetroxide complex to form HC(O)OH + •OH + HO2 •; (iii) A multi-step rearrangement of the initial HOCH2OOOOH tetroxide to yield HC(O)OH + O2(1Δ) + H2O, about twice as fast as the former channel on the singlet-surface. The findings provide an explanation for the observed hydroxyl radical formation in this reaction (Jenkin et al., Phys. Chem. Chem. Phys. 9 (2007) 3149) and rationalize the high overall rate and its pronounced negative temperature dependence (Veyret et al., J. Phys. Chem. 93 (1989) 2368).