Thiols and Disulfides on the Au(111) Surface: The Headgroup−Gold Interaction

• DOI: 10.1021/ja993622x
• Publication Date: 2002-07-26T05:56:09Z
• Authors: Henrik Grönbeck; Alessandro Curioni; Wanda Andreoni
• Keywords: Methanethiol; Cleavage (geology); Thiol

How thiols and disulfides bind to gold surfaces form self-assembled monolayers is a long-standing open question. In particular, determining the nature itself of anchor groups their interaction with metal priority issue, which has so far been approached only oversimplified models. We present ab initio calculations adsorption configurations (dissociative not) methanethiol dimethyl disulfide on Au(111) at low coverage, are based density functional theory using gradient-corrected exchange-correlation functionals. A complete characterization structure, binding energies, type bonding obtained. It established that dissociation clearly favored for subsequent formation strongly bound thiolates, in agreement experimental evidence, whereas thiolates resulting from S−H bond cleavage can coexist adsorbed "intact" species become if accompanied by molecular hydrogen.