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The local adsorption structure of methylthiolate in the ordered Au(111)-(sqrt[3]xsqrt[3])R30 degrees phase has been investigated using core-level-shift measurements of the surface and bulk components of the Au 4f(7/2) photoelectron binding energy. The amplitude ratio of the core-level-shift components associated with surface Au atoms that are, and are not, bonded to the thiolate is found to be compatible only with the previously proposed Au-adatom-monothiolate moiety in which the thiolate is bonded atop Au adatoms in hollow sites, and not on an unreconstructed surface, or in Au-adatom-dithiolate species.

Local Methylthiolate Adsorption Geometry on Au(111) from Photoemission Core-Level Shifts