S 2p photoabsorption of the SF5CF3 molecule: experiment, theory and comparison with SF6

9 pags, 4 figs, 2 tabsThe S 2p core excitation spectrum of the SF5CF3 molecule has been measured in the total ion yield mode. It resembles a lot the analogous spectrum of SF6, also recorded in this study, displaying intense transitions to the empty molecular orbitals both below and above the S 2p ionization potential (IP) and weak transitions to the Rydberg orbitals. The S 2p photoabsorption spectra of SF6 and SF5CF3 have been calculated using time-dependent density functional theory, whereby the spin-orbit coupling was included for the transitions below the S 2p IP. The agreement between experiment and theory is good for both molecules, which allows us to assign the main S 2p absorption features in SF5CF3. © 2010 Elsevier B.V. All rights reserved.We acknowledge the support provided by the European Community-Research Infrastructure Action under the FP6 ‘‘Structuring the European Research Area” Programme (through the Integrated Infrastructure Initiative ‘‘Integrating Activity on Synchrotron and Free Electron Laser Science”). A.K. and M.C. acknowledge the Italian National Research Council (CNR) for funding their research activityat the gas phase beamline, Elettra, under Projects MD.P06.016.002 (CNR-IOM) and MD.P03.026.001 (CNR-IMIP). A generous grant of computer time on the IBM SP6 of CINECA (Bologna, Italy) is gratefully acknowledged