Investigating the Association Reactions of HOCH₂CO and HOCHCHO with O₂: A Quantum Computational and Master Equation Study

Glycolaldehyde, HOCH₂CHO, is an important multifunctional atmospheric trace gas formed in the oxidation of ethylene and isoprene and emitted directly from burning biomass. The initial step in the atmospheric photooxidation of HOCH₂CHO yields HOCH₂CO and HOCHCHO radicals; both of these radicals react rapidly with O₂ in the troposphere. This study presents a comprehensive theoretical investigation of the HOCH₂CO + O₂ and HOCHCHO + O₂ reactions using high-level quantum chemical calculations and energy-grained master equation simulations. The HOCH₂CO + O₂ reaction results in the formation of a HOCH₂C(O)O₂ radical, while the HOCHCHO + O₂ reaction yields (HCO)₂ + HO₂. Density functional theory calculations have identified two open unimolecular pathways associated with the HOCH₂C(O)O₂ radical that yield HCOCOOH + OH or HCHO + CO₂ + OH products; the former novel bimolecular product pathway has not been previously reported in the literature. Master equation simulations based on the potential energy surface calculated here for the HOCH₂CO + O₂ recombination reaction support experimental product yield data from the literature and indicate that, even at total pressures of 1 atm, the HOCH₂CO + O₂ reaction yields ∼11% OH at 298 K.