Structure of SAM on Au(111)

Some of the most well known self-assembled monolayers (SAMs) are alkyl sulfides on gold surfaces. They have many potential applications in molecular electronics, biosensors, and nanopatterning. However, there have still been unsolved problems in basic research regarding Au-S interaction. Recently, Professor A. Morgante (Universita' di Trieste, Italy) and his colleagues published the results of grazing incidence X-ray diffraction and density functional theory-based molecular dynamics simulations for hexanethiol and methylthiol. The research group demonstrated surface complexes wherein two S atoms are joined by an intermediate Au adatom (RS-Au-SR) for longer chain cases. It was found that the sulfur atoms of the molecules bind at two distinct surface sites, and that the first surface layer contains vacancies as well as gold adatoms that are laterally bound to two sulfur atoms. Competition between SAM ordering and disordering of interfacial Au atoms takes an important role in the system. For more information, see the paper, "X-ray Diffraction and Computation Yield the Structure of Alkanethiols on Gold(111)", A. Cossaro et al., Science, 321, 943-946 (2008).