The adsorption structure of furan on Pd(111)

The structure of molecular furan, C4H4O, on Pd(1 1 1) has been investigated by O K-edge near-edge X-ray absorption fine structure (NEXAFS) and C is scanned-energy mode photoelectron diffraction (PhD). NEXAFS shows the molecule to be adsorbed with the molecular plane close to parallel to the surface, a conclusion confirmed by the PhD analysis. Chemical-state specific C 1s PhD data were obtained for the two inequivalent C atoms in the furan, the alpha-C atoms adjacent to the O atom, and the beta-C atoms bonded only to C atoms, but only the PhD modulations for the alpha-C emitters were of sufficiently large amplitude for detailed evaluation using multiple scattering calculations. This analysis shows the alpha-C atoms to be located approximately 0.6 angstrom off-atop surface Pd atoms with an associated C-Pd bondlength of 2.13 +/- 0.03 angstrom. Two alternative local geometries consistent with the data place the O atom in off-atop or near-hollow locations, and for each of these local structures there are two equally-possible registries relative to the fcc and hcp hollow sites. The results are in good agreement with earlier density functional theory calculations which indicate that the fcc and hcp registries are equally probable, but the PhD results fail to distinguish the two distinct local bonding geometries. (C) 2008 Elsevier B.V. All rights reserved.