Adsorption and Intermolecular Interaction of Cobalt Phthalocyanine on CoO(111) Ultrathin Films: An STM and DFT Study

We investigate the adsorption of cobalt phthalocyanine (CoPc) molecules on a thin layer of cobalt oxide grown on Ir(100). To that end we compare the results of low-temperature scanning tunneling microscopy (STM) with those of ab-initio density functional theory (DFT) calculations and reveal the adsorption geometry. We find that the CoPc molecules lie flat on the surface and that their central cobalt atom forms a chemical bond to a substrate oxygen ion. However, this bond contributes only modestly to the adsorption energy, while van-der-Waals forces dominate the potential landscape and determine to a large extend the geometry as well as the distortion of substrate and molecule. Furthermore they lead to attractive molecule-molecule interactions at higher molecular coverages. The DFT calculations predict energetic positions of the molecular orbitals which are compared to scanning tunneling spectroscopy (STS) measurements.