New insights in the c(4 x 2) reconstruction of hexadecanethiol on Au(111) revealed by grazing incidence X-ray diffraction.

The c(4 x 2) structure of C16H33SH alkanethiol monolayers self-assembled on Au(111) has been studied by grazing incidence X-ray diffraction. This structure coexists on the surface with the (radical3x radical3)R30 degrees phase. The structural refinement of the c(4 x 2) phase has been accomplished by omitting the fractional order reflections common to both structures. The surface unit cell consists of four symmetry-independent molecules with atomic displacements related by couples, such that only two nonequivalent chains are present in the surface cell. The stability between neighbor chains is due to van der Waals interactions. The substrate plays an important and non-negligible role in the c(4 x 2) reconstruction. The lateral and normal substrate relaxations to the surface plane are small, and gold atom displacements are lower than 0.25 angstroms but contribute very strongly to the fractional order intensities. The molecular chains form a close packed structure tilted by 37 degrees from the surface normal with no indications of dimer formation between closest S atoms.