title: Interfacial charge rearrangement and intermolecular interactions: Density-functional theory study of free-base porphine adsorbed on Ag(111) and Cu(111).
abstract: We employ dispersion-corrected density-functional theory to study the adsorption of tetrapyrrole 2H-porphine (2H-P) at Cu(111) and Ag(111). Various contributions to adsorbate-substrate and adsorbate-adsorbate interactions are systematically extracted to analyze the self-assembly behavior of this basic building block to porphyrin-based metal-organic nanostructures. This analysis reveals a surprising importance of substrate-mediated van der Waals interactions between 2H-P molecules, in contrast to negligible direct dispersive interactions. The resulting net repulsive interactions rationalize the experimentally observed tendency for single molecule adsorption.
authors.affiliation: Department Chemie, Technische Universität München, D-85747 Garching, Germany.
authors.forename: Moritz
authors.initials: M
authors.lastname: Müller
authors.affiliation: Department Chemie, Technische Universität München, D-85747 Garching, Germany.
authors.forename: Katharina
authors.initials: K
authors.lastname: Diller
authors.affiliation: Department Chemie, Technische Universität München, D-85747 Garching, Germany.
authors.forename: Reinhard J
authors.initials: RJ
authors.lastname: Maurer
authors.affiliation: Department Chemie, Technische Universität München, D-85747 Garching, Germany.
authors.forename: Karsten
authors.initials: K
authors.lastname: Reuter