Orbital and Skeletal Structure of a Single Molecule on a Metal Surface Unveiled by Scanning Tunneling Microscopy

Atomic-scale spatial characteristics of a phthalocyanine orbital and skeleton are obtained on a metal surface with a scanning tunneling microscope and a CO-functionalized tip. Intriguingly, the high spatial resolution of the intramolecular electronic patterns is achieved without resonant tunneling into the orbital and despite the hybridization of the molecule with the reactive Cu substrate. The resolution can be fine-tuned by the tip-molecule distance, which controls the p-wave and s-wave contribution of the molecular probe to the imaging process. The detailed structure is deployed to minutely track the translation of the molecule in a reversible interconversion of rotational variants and to quantify relaxations of the adsorption geometry. Entering into the Pauli repulsion imaging mode, the intramolecular contrast loses its orbital character and reflects the molecular skeleton instead. The assignment of pyrrolic-hydrogen sites becomes possible, which in the orbital patterns remains elusive.