Ab initio study of the reaction of propionyl (C2H5CO) radical with oxygen (O2)

The reaction of propionyl radical with oxygen has been studied using the full coupled cluster theory with the complete basis set. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for this important reaction in detail. The reaction takes place via a chemical activation mechanism. The barrierless association of propionyl with oxygen produces the propionylperoxy radical, which decomposes to form the hydroxyl radical and the three-center alpha-lactone predominantly or the four-center beta-propiolactone. The oxidation of propionyl radical to carbon monoxide or carbon dioxide is not straightforward rather via the secondary decomposition of alpha-lactone and beta-propiolactone. Kinetically, the overall rate constant is almost pressure independent and it approaches the high-pressure limit around tens of torr of helium. At temperatures below 600 K, the rate constant shows negative temperature dependence. The experimental yields of the hydroxyl radical can be well reproduced, with the average energy transferred per collision -DeltaE=20-25 cm(-1) at 213 and 295 K (helium bath gas). At low pressures, together with the hydroxy radical, alpha-lactone is the major product, while beta-propiolactone only accounts for about one-fifth of alpha-lactone. At the high-pressure limit, the production of the propionylperoxy radical is dominant together with a fraction of the isomers. The infrared spectroscopy or the mass spectroscopy techniques are suggested to be employed in the future experimental study of the C2H5CO+O2 reaction.