Perfluoro effects in the occupied and virtual valence orbitals of hexafluorobenzene

• Published in: Journal of physics. B, Atomic, molecular, and optical physics Atomic, molecular, and optical physics, 2007-07, Vol.40 (14), p.2939-2959
• Main Authors: Decleva, P, Stener, M, Holland, D M P, Potts, A W, Karlsson, L
• Format: Article
• Language: English
• Subjects: Ab initio calculations; Atomic and molecular physics; Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations); Electronic structure of atoms, molecules and their ions: theory; Exact sciences and technology; Fysik; Ionization potentials, electron affinities, molecular core binding energy; Molecular properties and interactions with photons; NATURAL SCIENCES; NATURVETENSKAP; Photoelectron spectra; Physics; Properties of molecules and molecular ions
• ISSN: 0953-4075; 1361-6455; 1361-6455
• DOI: 10.1088/0953-4075/40/14/012

The complete valence shell photoelectron spectrum of hexafluorobenzene has been recorded with synchrotron radiation and the observed structure has been interpreted using ab initio ionization energies and relative spectral intensities. The theoretical predictions for the single-hole ionic states due to outer valence shell ionization agree satisfactorily with the experimental results. Ionization from the inner valence, essential F 2s, orbitals is strongly influenced by many-body effects and the intensity is spread amongst numerous satellites. Photoelectron angular distributions and branching ratios have been determined both experimentally and theoretically, and demonstrate that shape resonances affect the valence shell photoionization dynamics. Some of the shape resonances have been associated with virtual valence orbitals. An assessment of the perfluoro effect on the occupied and virtual valence orbitals of hexafluorobenzene has been carried out by comparing the present results for C6F6 with similar data for C6H6.