Pauli Repulsion Versus van der Waals: Interaction of Indenocorannulene with a Cu(111) Surface

Modification of metal electrode surfaces with functional organic molecules is an important step toward organic electronics. The interaction of the buckybowl indenocorannulene with a Cu(111) surface and the two-dimensional self-assembly on the same surface was studied by means of scanning tunneling microscopy and dispersion-enabled density functional theory. Based on the conjecture of maximizing van der Waals interaction with the surface one would expect the indeno group to be aligned parallel to the surface. Theoretical investigations predict a nonparallel arrangement with the benzo ring of the indeno group located higher above the surface than the bowl rim connected to the indeno group. This adsorbate geometry is due to strong electronic interaction between molecule and surface, including substantial Pauli repulsion. The long-range ordered monolayer shows differences for two molecules of the unit cell in scanning tunneling microscopy contrast, suggesting either different polar alignments, and therefore a...