A theoretical study of the structures and vibrational spectra of dioxirane and difluorodioxirane

Calculations at the 3-21G and 3-21G^(*) level of ab initio SCF theory have been performed to predict the geometries, harmonic frequencies and infrared intensities of dioxirane and difluorodioxirane. A scaling-factor procedure has been employed to provide better estimates of the as yet experimentally undetermined vibrational spectra of these species. The posssible presence of dioxirane along with 1,2,3-trioxolane, as the initial products of ethylene ozonolysis at low temperature is discussed, as is the possible intermediacy of difluorodioxirane in low-pressure pyrolysis of bis-(trifluoromethyl) peroxide and in ozonolysis of perfluoroethylene.