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Carlos J. Cobos, A.E. Croce

Evidences for a new Ultraviolet Absorption Band of the FSO₃ Radical

Keywords: Absorption Spectra, FSO3 Radical, TD-DFT Calculations

An unpublished absorption band of the fluorosulphate radical, FSO₃, based on earlier experiments of Schumacher and co-workers (Z. Phys. Chem. NF 42 (1964) 174) and detailed calculations of the whole FSO₃ 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 275nm, has been extracted from an absorption spectrum taken from equilibrated mixtures of FSO₃ with the dimer FS(O₂)OO(O₂)SF at 403K. 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 FSO₃ band system.

Zeitschrift für Physikalische Chemie, Oldenbourg Wissenschaftsverlag

Print ISSN: 0942-9352
Volume: 221, 07/2007
Pages: 897 - 909

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