Adsorption modes of cysteine on Au(111): Thiolate, amino-thiolate, disulfide

The adsorption of cysteine on the ?111? surface of gold has been studied by means of periodic supercell density-functional theory calculations. A number of different adsorption modes are examined, including adsorption through the thiol group in either thiolate or disulfide form, and adsorption through both the thiol and amino functional groups. We find that at intermediate coverage densities the latter mode of adsorption is favored, followed by thiolate adsorption at the bridge ?slightly displace toward fcc? site. The N-Au and S-Au bond strengths in the amino-thiolate adsorption are estimated to be of the order of 6 and 47 kcal/mol, respectively. The electronic structure of the different systems is analyzed, with focus on the total and projected density of states, as well as on the detailed character of the electronic states at the interface. States near the Fermi energy are found to have a metal-molecule antibonding character, whereas metal-molecule bonding states mostly occur near the lower edge of the Au-d band.