Experimental Determination of the Excited-State Polarizability and Dipole Moment in a Thin Organic Semiconductor Film

We report the evolution of the electronic structure of excited (sub)monolayer films of vanadyl naphthalocyanine (VONc) at the interface with highly oriented pyrolytic graphite (HOPG). Using two-photon photoemission spectroscopy, an unoccupied state corresponding to the lowest unoccupied molecular orbital of VONc is observed. The energy of this state shows a significant dependence on coverage, interpreted in the context of the electrostatic environment at the interface. On the basis of a simple electrostatic model, we were able to determine the excited-state polarizability and dipole moment of VONc at the interface with HOPG. The results suggest that local electric fields may have a major influence on interfacial energy level alignment in the excited-state manifold, with direct consequences for interfacial charge-transfer dynamics.