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Surface-induced optimal packing of two-dimensional molecular networks.

Authors
Type
Published Article
Journal
Physical Review Letters
1079-7114
Publisher
American Physical Society
Publication Date
Volume
114
Issue
6
Pages
66101–66101
Identifiers
PMID: 25723230
Source
Medline

Abstract

High-density packing in organic crystals is usually associated with an increase of the coordination between molecules. Such a concept is not necessarily extended to two-dimensional molecular networks self-assembled on a solid surface, for which we demonstrate the key role of the surface in inducing the optimal packing. By a combination of scanning tunneling microscopy experiments and multiscale computer simulations, we study the phase transition between two polymorphs. We find that, contrary to intuition, the structure with the lowest packing fraction corresponds to the highest molecular coordination number, due to the competition between surface and intermolecular forces. Having the lowest free energy, this structure spreads out as the most stable polymorph over a wide range of molecular concentrations.

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