Measurements of the core-level shifts in Au 4f photoemission spectra from Au(1 1 1) at different coverages of methylthiolate and butylthiolate are reported. Adsorption leads to two components in addition to that from the bulk, one at lower photoelectron binding energy attributed to surface atoms not bonded to thiolate species, while the second component has a higher binding energy and is attributed to Au atoms bonded to the surface thiolate. The relative intensities of these surface components for the saturation coverage (mainly (√3 × √3)R30°) phases are discussed in terms of different local adsorption sites in a well-ordered surface, and favour adsorption of the thiolate species atop Au adatoms. Alternative interpretations that might be consistent with an Au-adatom-dithiolate model are discussed, particularly in the context of the possible influence of reduced coverage associated with a disordered surface. Marked differences from previously-reported results for longer-chain alkylthiolate layers are highlighted
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