Matrix isolation study of S2O6F2 pyrolysis products: The infrared spectrum of SO3F radical

Infrared and visible absorption spectra of the low pressure heated products of S₂O₆F₂ trapped in inert gas matrices at 14 K are presented. The following have been identified as major infrared-absorbing species: SO₃F, SO₃, HSO₃F, and S₂O₆F₂, with matrix spectra of the latter three unequivocally confirming their presence. Reasonable reactions accounting for the production of these species are proposed, and a reassignment of the fundamental vibrations of monomeric HSO₃F is offered. The infrared absorptions of the SO₈F radical have been observed for the first time, and the six fundamental vibrations determined. These frequencies are in good accord with earlier values deduced indirectly by King and Warren from hot band transitions in the visible absorption spectrum of the vapor. This same visible system (${}^2\text{E}\text{-}\text{X}\text{?}{}^2\text{A}{}_2$) has also been observed here for the matrix isolated species.