c(4x2) structures of alkanethiol monolayers on Au (111) compatible with the constraint of dense packing.

Using alkanethiol dense packing as a starting point, we have found six prototypical packing structures commensurate with the (3x2 radical3) supercell of the Au (111) surface. Five of the six structures are not compatible with the flat surface conditions but can be fitted to a reconstructed surface. Combined with density functional theory calculations and simulations of grazing incidence X-ray diffraction maps and of scanning tunneling microscopy images, this allowed us to refine and assess the recently proposed models of the c(4x2) self-assembled monolayers involving thiolate-adatom and thiolate-adatom-thiolate species and to propose a new model with four gold adatoms per unit cell.