Theoretical study on the comparative fate of the 1-butoxy and β-hydroxy-1-butoxy radicals
Abstract
Theoretical
high level ab initio BAC-MP4 and DFT calculations followed by a kinetic RRKM analysis have been performed
in this work for the study of unimolecular reactions of the 1-butoxy and β-hydroxy-1-butoxy radicals. We have
shown that the substitution of H by OH on the carbon in the β position of the 1-butoxy radical (leading to the
β-hydroxy-1-butoxy radical) results in an important lowering of the decomposition barrier and a slight increase of the
isomerisation barrier. Coupled to the rate constant calculations, this study suggests that, contrary to the fate
of the 1-butoxy radical, the thermal decomposition is the major pathway for the β-hydroxy-1-butoxy radical. We
have also shown that, under atmospheric conditions (760 Torr and 298 K), both isomerisation and decomposition processes
are still in the fall-off range for the