Understanding Structure and Bonding of Multilayered Metal−
Organic Nanostructures

For organic and hybrid electronic devices, the physicochemical properties
of the contained interfaces play a dominant role. To disentangle the various interactions
occurring at such heterointerfaces, we here model a complex, yet prototypical, threecomponent system consisting of a Cu−phthalocyanine (CuPc) film on a 3,4,9,10-perylenetetracarboxylic-dianhydride (PTCDA) monolayer adsorbed on Ag(111). The two
encountered interfaces are similar, as in both cases there would be no bonding without
van der Waals interactions. Still, they are also distinctly different, as only at the Ag(111)−
PTCDA interface do massive charge-rearrangements occur. Using recently developed
theoretical tools, we show that it has become possible to provide atomistic insight into the
physical and chemical processes in this comparatively complex nanostructure distinguishing between interactions involving local rearrangements of the charge density and longrange van der Waals attraction.