Ab Initio Studies of Ag–S Bond Formation during the Adsorption of l‑Cysteine on Ag(111)

Ab initio studies of Ag–S bond formation during the adsorption of l-cysteine on Ag(111) have been performed by combining density functional theory with a quantum mechanical model developed in our group. The adsorbate–silver bond formation has been investigated by analyzing the projected density of states onto the different atoms of the molecule and by charge density difference calculations when the zwitterion radical approaches the surface. The polar character of the bond can be distinguished. For the first time, the coupling constants of the sulfur orbitals with the d and sp bands have been calculated by fitting the density of states. The role of the sp bands in the stabilization of the sulfur–silver bond is analyzed. The differences with the catalysis of hydrogen adsorption are discussed. Copper, gold, and silver are not good catalysts for the adsorption of hydrogen because of the position of the d bands lying too far below the Fermi level. However, the coin metals are excellent for the adsorption of thiols. The reason is that at the equilibrium position the sulfur atom is much farther from the surface than hydrogen, and thus the interactions with the sp bands stabilize its bond to the surface