Bond polarization and image-potential screening in adsorbed C6F6 on Cu(1 1 1)

The orientation of hexafluorobenzene (C₆F₆) on the Cu(1 1 1) surface has been determined for different coverages with the help of near edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). The adsorption geometry and the bonding mode of C₆F₆ differ significantly in comparison to its hydrocarbon analog C₆H₆. C₆F₆ is found to adsorb on Cu(1 1 1) with the ring plane parallel to the surface for coverages below 10 ML. Next to the distinct multilayer, bilayer and monolayer phases we also present evidence of sub-monolayer (i.e., 1/2 ML) coverage with different electronic structure. These findings are explained in a phenomenological model based on fluorine’s property as a σ-acceptor and a π-donor and the resulting bond polarization within the molecule, which is stabilized by image-potential screening within the substrate.