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

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 127; no. 19; pp. 4302 - 4316
• Main Authors: Lockhart, J. P. A., Bodipati, B., Rizvi, S.
• Format: Journal Article
• Language: English
• Published: American Chemical Society 18-05-2023
• Subjects: A: Aerosols; Environmental and Atmospheric Chemistry; Astrochemistry
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.2c08163

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.