A theoretical study on the thermodynamic properties of the formation and decomposition of methyloxirane via triplet mechanisms

Abstract

Molecular unrestricted Hartree-Fock calculations with geometry optimization have been carried out on eight triplet isomers of C 3H 6O considered to be possible intermediates in the addition of O( 3P) atoms to propylene and in the Hg( 3P) sensitization of methyloxirane. The computed thermodynamic stabilities reveal that four triplet states are available in the former and eight triplet states are available in the latter reaction. The isomer CH 3ĊHCH 2Ȯ is more stable than ȮCHCH 3ĊH 2. This latter feature gives a satisfactory explanation for the experimental observation that in the O( 3P) + C 3H 6 reaction propionaldehyde is the major carbonyl product.