Delocalized electron resonance at the alkanethiolate self-assembled monolayer/Au(111) interface

We probe the electronic structure of alkanethiolate self-assembled monolayers (SAMs) on Au(111) using two-photon photoemission spectroscopy. We observe a dispersive unoccupied resonance close to the vacuum level with a lifetime shorter than 30 fs. The short lifetime and the insensitivity of the energy level and dispersion to molecular length (and thus layer thickness) suggest that the probability density of the electron wave function is concentrated inside the molecular layer close to the SAM/Au interface. Such an interfacial resonance results from the image like potential at the SAM/Au interface.