Structural and electronic properties of ultrathin picene films on the Ag(100) surface

Abstract Using scanning tunneling microscopy and electronic structure calculations, we investigated the assembly and electronic properties of picene molecules on the Ag(100), Ag(111), and Cu(111) surfaces, with particular emphasis on Ag(100). In each case, picene molecules are found to lie parallel to the surface at coverages up to half a monolayer and to adopt alternating parallel and tilted orientations at full monolayer coverage. In the latter case, the arrangement of the molecules is roughly similar to that in the bulk crystal. On the metal surfaces considered, the growth mode of picene is quite different from that of its structural isomer pentacene, which forms a bilayer overlayer on top of a dense monolayer of flat-lying molecules on metal surfaces. Tunneling spectroscopy measurements provide estimates of the energies of several low-lying unfilled molecular orbitals as well as of the highest occupied molecular orbital of the absorbed picene molecules. From analysis of these results, we establish that the on-site Coulomb repulsion for picene decreases by ~ 2 eV in going from the gas phase to the full monolayer on Ag(100), bringing it close to that of the undoped bulk crystal.