Modeling thiols on Au(111): Structural, thermodynamic and magnetic properties of simple thiols and thiol-radicals

Self-assembled monolayers (SAMs) of functionalized organic/inorganic moieties represent one of the new trends in nanoscience. The most representative models for SAMs are those where saturated and unsaturated thiols on gold surfaces are involved. To give an insight on the site of attack and the reacting species involved in the reactions we have performed mixed gaussian/planewaves periodic DFT calculations on the absorption of simple Me–SX (X=H,−, and ⋅) species on the Au(111). A bridge-fcc binding site has been confirmed on clear gold surfaces but a more exothermic reaction has been encountered when a reconstructed (adatoms) surface has been considered. Moreover, preliminary and encouraging results on structural and magnetic data on SAMs of the 4-(methylthio)phenyl nitronyl nitroxide and the 4-(methylthio)methyl phenyl nitronyl nitroxide on the Au(111) will be also presented.