Interfacial charge rearrangement and intermolecular interactions: Density-functional theory study of free-base porphine adsorbed on Ag(111) and Cu(111)

Moritz Müller; Katharina Diller; Reinhard J Maurer; Karsten Reuter

doi:10.1063/1.4938259

Interfacial charge rearrangement and intermolecular interactions: Density-functional theory study of free-base porphine adsorbed on Ag(111) and Cu(111)

J Chem Phys. 2016 Jan 14;144(2):024701. doi: 10.1063/1.4938259.

Authors

Moritz Müller¹, Katharina Diller¹, Reinhard J Maurer¹, Karsten Reuter¹

Affiliation

¹ Department Chemie, Technische Universität München, D-85747 Garching, Germany.

PMID: 26772581
DOI: 10.1063/1.4938259

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.

Publication types

Research Support, Non-U.S. Gov't