van der Waals Interaction Activated Strong Electronic Coupling at the Interface between Chloro Boron-Subphthalocyanine and Cu(111)

[Image: see text] In this article, we investigate the interface between shuttlecock-shaped chloro boron-subphthalocyanine molecules and the Cu(111) surface. We highlight how molecular planarization induced by van der Waals forces can fundamentally alter the interface properties and how it can enable a particularly strong hybridization between molecular and metal states. In our simulations, we start from a situation in which we disregard van der Waals forces and then introduce them gradually by rescaling the interaction parameter, thereby “pulling” the molecule toward the surface. This reveals two adsorption regimes with significantly different adsorption distances, molecular conformations, and adsorbate-induced changes of the work function. Notably, the above-mentioned massive hybridization of electronic states, also observed in photoelectron spectroscopy, is obtained solely for one of the regimes. We show that this regime is accessible only as a consequence of the planarization of the molecular backbone resulting from the van der Waals attraction between the molecule and the surface. The results of this study indicate that for certain metal–molecule combinations unusually strong interfacial electronic interactions can be triggered by van der Waals forces creating a situation that differs from the usually described cases of physisorptive and chemisorptive interactions.