The outer valence shell photoelectron spectrum of CF3SF5 has been studied experimentally and theoretically. Synchrotron radiation has been used to record angle-resolved outer valence shell photoelectron spectra of CF3SF5 in the photon energy range 18–60 eV. These spectra have allowed photoelectron asymmetry parameters and branching ratios to be derived. The Outer Valence Green's Function approach has been employed to calculate the molecular orbital configuration and associated binding energies. A charge distribution analysis has also been obtained. Assignments have been proposed for the peaks observed in the photoelectron spectrum. The absolute photoabsorption cross section of CF3SF5 has been measured from threshold to 40 eV, and strongly resembles that of SF6. Assignments, involving intravalence transitions, have been proposed for some of the principal features appearing in the photoabsorption spectrum of CF3SF5.
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