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.
- Publication:
-
Journal of Chemical Physics
- Pub Date:
- January 2016
- DOI:
- 10.1063/1.4938259
- arXiv:
- arXiv:1512.01987
- Bibcode:
- 2016JChPh.144b4701M
- Keywords:
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- Physics - Chemical Physics;
- Condensed Matter - Materials Science
- E-Print:
- 16 pages, 8 figures, 3 tables