Benzene on Cu(111): II. Molecular assembly due to Lateral van der Waals and Surface-State-Mediated Indirect Interactions

Experiments show that benzene condenses into two different structural phases: a compact and a sparse phase, both of approximately hexagonal symmetry. The vdW-DF calculations demonstrate that the denser benzene-overlayer phase, with lattice constant 6.74 \AA, is due to direct benzene-benzene vdW attraction. The structure of the second, sparser phase, with lattice spacing 10.24 \AA, is attributed to the indirect electronic interactions mediated by the well-known metallic surface state on Cu(111). To support this claim, we use a formal Harris-functional approach to evaluate nonperturbatively the asymptotic form of this indirect interaction. Our extended vdW-DF scheme---which combines calculations of molecular physisorption, of direct intermolecular vdW coupling, and of indirect electronic interactions between the molecular adsorbates---accounts well for the structural phases of benzene on Cu(111). Our preliminary vdW-DF study of acene and quinone interactions provides building blocks for modeling of anthraquinone assembly on Cu(111).\footnote{G. Pawin, $\ldots$, L. Bartels, Science 313 (2006) 961}