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An unpublished absorption band of the fluorosulphate radical, FSO 3 , based on earlier experiments of Schumacher and co-workers (Z. Phys. Chem. NF  42  (1964) 174) and detailed calculations of the whole FSO 3  spectra based on the time-dependent (TD) generalization of the density functional theory (DFT), TD-DFT, are reported. Part of this band, that increases in intensity at wavelengths below 275 nm, has been extracted from an absorption spectrum taken from equilibrated mixtures of FSO 3  with the dimer FS(O 2 )OO(O 2 )SF at 403 K. A set of thirteen exchange-correlation hybrid functionals combined with the 6-311+G(3df) basis set predict an intense absorption band centred at 256 ± 10nm in very good agreement with the experimental observations. Another significant band peaked at 184 ± 10nm was also found. The calculations reproduce accurately the position of the maximum and the experimental oscillator strength of the well-known visible FSO 3  band system.

Evidences for a new Ultraviolet Absorption Band of the FSO 3 Radical