Theoretical Study of the Kinetics and Mechanism of the Thermal Decomposition of 3-Oxetanone in the Gas Phase

Abstract

The kinetics and mechanism of the thermal decomposition reaction of 3-oxetanone in the gas phase were studied using quantum chemical calculations. The major products of this reaction are formaldehyde, ketene, carbon monoxide, ethylene oxide, ethylene and methyl radical. Formaldehyde, ketene, carbon monoxide and ethylene oxide are the initial decomposition products and other species are the products of ethylene oxide decomposition. The results of B3LYP and QCISD(T) calculations reveal that thermal decomposition of 3-oxetanone to ethylene oxide and carbon monoxide is more probable than to formaldehyde and ketene from an energy viewpoint. Moreover, quantum theory of atoms in molecules and natural bond orbital analysis indicate that 3-oxetanone decomposition to formaldehyde, ketene, carbon monoxide and ethylene occurs via a concerted mechanism and bonds that are involved in the transition states have a covalent character. Moreover, the calculated changes in bond lengths in the transition states reveal that bond breaking and new bond formation occur asynchronously in a concerted mechanism.