Photoelectron spectroscopy of sulfur L levels in the SF5CF3 molecule

The photoelectron spectra of the S 2s and S 2p main lines as well as of the S 2p shake-up satellites of the SF5CF3 molecule have been measured using synchrotron radiation excitation. The main spectral lines have been compared to those of the closely-related SF6 molecule. The S 2p binding energies in SF5CF3 were obtained in reference to those in SF6, while the S 2s binding energies of both SF5CF3 and SF6 were determined with respect to the Ar 2p-(1) states. The intensity behavior of the spin-orbit-split S 2p photoelectron lines of SF5CF3 was studied in the region of the shape resonance whose maximum is located some 15 eV above the S 2p threshold. The S 2p shake-up satellite spectrum of SF5CF3 has been interpreted with the aid of ab initio configuration interaction calculations within the sudden-limit approximation. (C) 2008 Elsevier B.V. All rights reserved.