Competing thermodynamic and dynamic factors select molecular assemblies on a gold surface

Abstract

Controlling the self-assembly of surface-adsorbed molecules into nanostructures requires understanding physical mechanisms that act across multiple length and time scales. By combining scanning tunneling microscopy with hierarchical ab initio and statistical mechanical modeling of 1,4-substituted benzenediamine (BDA) molecules adsorbed on a gold (111) surface, we demonstrate that apparently simple nanostructures are selected by a subtle competition of thermodynamics and dynamics. Of the collection of possible BDA nanostructures mechanically stabilized by hydrogen bonding, the interplay of intermolecular forces, surface modulation, and assembly dynamics select at low temperature a particular subset: low free energy oriented linear chains of monomers, and high free energy branched chains.

arXiv comment6 pages, 4 figures

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Cited by in corpus (4)

• Energy Level Alignment at Molecule-Metal Interfaces from an Optimally-Tuned Range-Separated Hybrid Functional
• Examples of molecular self-assembly at surfaces
• Energy Level Alignment at Hybridized Organic-metal Interfaces: the Role of Many-electron Effects
• Polyomino Models of Surface Supramolecular Assembly: Design Constraints and Structural Selectivity