Metal d-orbital occupation-dependent images in the scanning: Tunneling microscopy of metal phthalocyanines

A strong d-orbital dependence in the scanning tunneling microscopy image of metal phthalocyanines is demonstrated. Unlike copper phthalocyanine (CuPc) wherein the central metal appears as a hole in the molecular image, the cobalt atom in CoPc is the highest point (about 0.3 nm) in the molecular image. On the other hand, the benzene ring regions of CoPc and CuPc appear to have the same height. These data are consistent with theoretical calculations that predict a large contribution of cobalt d-orbitals near the Fermi energy. An intriguing aspect of this work is that it may be possible to chemically identify the different metal phthalocyanines simply by their appearance. This is demonstrated for the case of a mixed monolayer of CuPc and CoPc on Au(111).