The Adsorption of Methanethiol and Benzenethiol on Silver Surfaces

The Adsorption of Methanethiol and Benzenethiol on Silver Surfaces

The adsorption of methanethiol and benzenethiol on Ag(111) and Ag(100) surfaces is studied respectively, employing ASED (Atom Superposition and Electron Delocalization) method. Metal surfaces are modelled by 3-layer clusters. The corresponding thiolate anions are taken as adsorbates. The highly coordinated binding sites are most favored for both surfaces. The tilted angles of C-S axis from the surface normal are nearly zero. There's Charge transfer from adsorbate to substrate and the stretching frequency of C-S bond upon adsorption is blue-shifted from its gas phase counterpart, and its amount is the smallest at most highly coordinated site. FMO (Fragment Molecular Orbital) analysis of the system give the explanation for these results.