Molecular alligator clips: a theoretical study of adsorption of S, Se and S–H on Au(111)

For the binding of thiols to Au, the Au–S interaction is decisive for the geometry, bonding strength and transmissivity of the metal–molecule interface. Using ab initio methods we investigate the adsorption of sulfur (S) on the Au(111) surface for different coverages between 0.25 and 1.0 monolayers (ML). Corresponding geometries with adsorbed Se are included to establish possible differences between S- and Se-based metal–molecule interfaces. We furthermore investigate hydrogenation of sulfur-covered Au(111) surfaces to establish the energetics and resulting geometry of adsorption of S–H groups on clean Au(111), using it as a simple model system. For the relatively low coverage of 0.25 ML the S and Se atoms are found to prefer the in-hollow sites, with Se displaying a substantially stronger bond. Increasing the coverage leads to depletion of available free charge in the gold surface, which weakens the bonds to the S (Se). Due to the more extensive hybridization, Se is more insensitive to the exact geometry, and the stacking fault position only costs 0.04 eV. At even higher coverage (0.75 ML) the adsorbed atoms hybridize internally and form triatomic molecules situated on top of the Au surface atoms. In S (Se) rich environments this turns out to be the most stable configuration investigated, while in S (Se) poor conditions the surface will adsorb all available S (Se). Forcing the system to adsorb atoms beyond this coverage increases the total energy. For all physically realizable coverages the Au–Se bond is found to be ≥0.25 eV stronger than the corresponding Au–S bond. The Se bond also displays a higher degree of metallicity and should be expected to make a better head group for thiols, for example; this is relevant for both bonding and conductivity. Turning to the hydrogenated S systems we find that surfaces with a high coverage of S only weakly bind H at low partial hydrogenation, while H adsorption in systems with medium and low S concentrations is found to be energetically stable by around 0.3 eV per H atom. The adsorption geometry is sensitive to the concentration: exposed to free S, the system will increase the S coverage and expel H.