Electronic and Vibrational States of Single Tin-Phthalocyanine Molecules in Double Layers on Ag(111)

Electronic and vibrational properties of the two stable molecular configurations of Sn-phthalocyanine adsorbed on an ultrathin Sn-phthalocyanine buffer film on Ag(111) have been investigated with scanning tunneling microscopy and density functional calculations. Complex submolecular patterns are experimentally observed in unoccupied states images. The calculations show that they result from a superposition of n p-orbitals.Furthermore, the characteristic features in spectra of the differential conductance are reproduced by the calculations together with a remarkable difference between the two configurations. First-principles calculations show that rather than a single vibrational mode and its higher harmonics the excitations of different molecular vibrational quanta induce replica of orbital spectroscopic signatures. The replicated orbital features appear for the configuration with a low molecule-surface coupling. Spectra of molecules with a larger coupling to the surface are described by considering elastic tunneling to orbital resonances alone