Rich Coordination Chemistry of Au Adatoms in Gold Sulfide Monolayer on Au(111)
- 26 July 2006
- journal article
- Published by American Chemical Society (ACS) in The Journal of Physical Chemistry B
- Vol. 110 (32), 15663-15665
- https://doi.org/10.1021/jp0641379
Abstract
The rich chemistry of Au nanoparticles and ions has attracted tremendous interest, in part because the surfaces of bulk Au have traditionally been considered to be chemically inert. On the other hand, large-scale mass transport and the formation of vacancy islands have been observed on the Au(111) surface following the deposition of adsorbates, such as sulfur and thiols, that can interact strongly with the Au surface. In this work, we revisit the structure and chemistry of an ordered incommensurate AuS adlayer that forms on Au(111) following the deposition of sulfur and annealing to 450 K. A structural model of this AuS surface phase has not yet been determined experimentally due to the complexity of the system. Here, we use state-of-the-art density functional theory to develop an atomic-scale model that is consistent with the previously reported Au−S stoichiometry. In particular, we introduce theoretical techniques to take into account the charge transfer in an incommensurate system. Our model reproduces convincingly STM images and is remarkably robust. Bonding analysis based on Wannier functions shows that the model exhibits rich coordination chemistry corresponding to different Au oxidation states. The extraordinary stability and rich chemistry of this structure have implications for related S−Au interfaces and previously reported surface features of this system.Keywords
This publication has 14 references indexed in Scilit:
- Localized orbital description of electronic structures of extended periodic metals, insulators, and confined systems: Density functional theory calculationsPhysical Review B, 2006
- Enhancement of O2 Dissociation on Au(111) by Adsorbed Oxygen: Implications for Oxidation CatalysisJournal of the American Chemical Society, 2005
- Self-Assembled Monolayers of Thiolates on Metals as a Form of NanotechnologyChemical Reviews, 2005
- Revisiting the S−Au(111) Interaction: Static or Dynamic?Langmuir, 2005
- Theoretical Chemistry of GoldAngewandte Chemie-International Edition, 2004
- Following Adsorption Kinetics at Electrolyte/Metal Interfaces through Crystal Truncation Scattering: Sulfur on Au(111)Physical Review Letters, 2003
- Structure and electrical properties of Au2SSolid State Ionics, 1995
- Why gold is the noblest of all the metalsNature, 1995
- Observing surface chemical transformations by atomic-resolution scanning tunneling microscopy: sulfide electrooxidation on gold(111)The Journal of Physical Chemistry, 1992
- Gold(III) oxideActa Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 1979