Rings sliding on a honeycomb network: Adsorption contours, interactions, and assembly of benzene on Cu(111)

Using a van der Waals density functional vdW-DF Phys. Rev. Lett. 92, 246401 2004 , we perform ab initio calculations for the adsorption energy of benzene Bz on Cu 111 as a function of lateral position and height. We find that the vdW-DF inclusion of nonlocal correlations responsible for dispersive interactions changes the relative stability of eight binding-position options and increases the binding energy by over an order of magnitude, achieving good agreement with experiment. The admolecules can move almost freely along a honeycomb web of “corridors” passing between fcc and hcp hollow sites via bridge sites. Our diffusion barriers for dilute and two condensed adsorbate phases are consistent with experimental observations. Further vdW-DF calculations suggest that the more compact hexagonal Bz-overlayer phase, with lattice constant a =6.74 Å, is due to direct Bz-Bz vdW attraction, which extends to 8 Å. We attribute the second, sparser hexagonal Bz phase, with a=10.24 Å, to indirect electronic interactions mediated by the metallic surface state on Cu 111 . To support this claim, we use a formal Harris-functional approach to evaluate nonperturbationally the asymptotic form of this indirect interaction. Thus, we can account well for benzene self-organization on Cu 111 .