The electron spin resonance spectra of randomly oriented trifluoromethyl radicals in rare-gas matrices at low temperatures

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Abstract
The electron spin resonance spectra of u.v.-irradiated CF3I in various rare gas matrices at 4·2°k have been studied and interpreted in terms of randomly oriented, non-inverting .CF3 radicals with nearly axial hyperfine couplings whose axes make an angle close to that of the out-of-plane perpendiculars to the C-F bonds. A second-order treatment is required in the explanation of the line-shapes. The temperature dependence of the spectra has been investigated and it is shown that with increasing temperature the .CF3 radicals begin rotating and recombining, while some combine with traces of oxygen to give a non-rotating, peroxyl-type radical.