Observation of a molecule-metal interface charge transfer state by resonant photoelectron spectroscopy

We report the discovery of a novel charge transfer (CT) state at a molecule-metal interface by the application of resonant photoelectron spectroscopy (ResPES). This interface feature is neither present for molecular bulk samples nor for the clean substrate. Within a simplified two-step model this signal is assigned to a particular final state that is invisible in direct photoelectron spectroscopy but in ResPES revealed through relative resonant enhancement. A detailed analysis of the spectroscopic signature of the CT state shows characteristics of electronic interaction not found in other electron spectroscopic techniques. Our study demonstrates the sensitivity of ResPES to such interactions and constitutes a new way to investigate CT at molecule-metal interfaces.