Character of Electronic States in the Transport Gap of Molecules on Surfaces.

We report on scanning tunneling microscopy (STM) topographs of individual metal phthalocyanines (MPc) on a thin salt (NaCl) film adsorbed on a gold substrate, at tunneling energies within the molecule's electronic transport gap. Theoretical models of increasing complexity are discussed. The calculations for MPcs adsorbed on a thin NaCl layer on Au(111) demonstrate that the STM pattern rotates with the molecule's orientations─in excellent agreement with the experimental data. Thus, even the STM topography obtained for energies in the transport gap represent the structure of a one atom thick molecule. It is shown that the electronic states inside the transport gap can be rather accurately approximated by linear combinations of bound molecular orbitals (MOs). The gap states include not only the frontier orbitals but also surprisingly large contributions from energetically much lower MOs. These results will be essential for understanding processes, such as exciton creation, which can be induced by electrons tunneling through the transport gap of a molecule.