Mechanism and dynamics of the CH2OH+O2 reaction

Quantum mechanical calculations using B3LYP functional and the CBS-QB3 approach are used to determine the critical points on the potential energy surface for the reaction of (CH2OH)-C-. with O-2, and RRKM-Master Equation calculations are used to follow the time history of the intermediates. The HOCH2OO radical is bound by 35.8 kcal/mole and the barrier for the stabilized adduct forming a CH2=O-HO2 complex is only 13.6 kcal/ mole. At 298 K in 760 Torr of N-2, the chemically activated HOCH2OO' that does not promptly fall apart to reactants will be entirely transformed to CH2O+HO2 within 50 ps. (C) 2002 Published by Elsevier Science B.V.