title: The role of gold adatoms and stereochemistry in self-assembly of methylthiolate on Au(111).
abstract: On the basis of high resolution STM images and DFT modeling, we have resolved low- and high-coverage structures of methylthiolate (CH(3)S) self-assembled on the Au(111) surface. The key new finding is that the building block of all these structures has the same stoichiometry of two thiolate species joined by a gold adatom. The self-arrangement of the methylthiolate-adatom complexes on the surface depends critically on their stereochemical properties. Variations of the latter can produce local ordering of adatom complexes with either (3 x 4) or (3 x 4 square root(3)) periodicity. A possible structural connection between the (3 x 4 square root(3)) structure and commonly observed (square root(3) x square root(3))R30 degrees phase in methylthiolate self-assembled monolayers is developed by taking into account the reduction in the long-range order and stereochemical isomerization at high coverage. We also suggest how the observed self-arrangements of methylthiolate may be related to the c(4 x 2) phase of its longer homologues.
authors.affiliation: Department of Electrical and Computer Engineering, Centre of Excellence for Information Engineering (CEGI), Université de Sherbrooke, Sherbrooke, Québec J1K 2R1, Canada. o.voznyy@usherbrooke.ca
authors.forename: Oleksandr
authors.initials: O
authors.lastname: Voznyy
authors.forename: Jan J
authors.initials: JJ
authors.lastname: Dubowski
authors.forename: J T
authors.initials: JT
authors.lastname: Yates
authors.forename: Peter
authors.initials: P
authors.lastname: Maksymovych