Photoelectron study of the valence level cross sections of XeF2 from 21 to 50 eV photon energy

Using monochromatized synchrotron radiation, the gas phase photoelectron spectra of the first five valence orbitals of XeF2 have been obtained from 21–50 eV photon energy. From these spectra, the branching ratios and partial cross sections have been calculated. Theoretical branching ratios and partial cross sections have been obtained from MS-Xα calculations and compared with experiment. The generally good agreement between experiment and theory confirms the DV-Xα and MS-Xα orbital assignments: 5πu <10σg <3πg <4πu <6σu, in order of increasing binding energy. Somewhat surprisingly because of the lack of antibonding virtual orbitals above threshold and the long Xe–F bond length (2.00 Å), a number of strong resonances are predicted and observed. For example, resonances are predicted at 4.8 (πg channel), 11.6 (πu, δu channels), and 14.3 eV (σu channel) kinetic energies. The observed resonance positions are usually in reasonable agreement with these. The nature of these resonances are discussed, and compared to similar features in O2, F2, and CO2.