Increasing the Templating Effect on a Bulk Insulator Surface: From a Kinetically Trapped to a Thermodynamically More Stable Structure

Paris C, Floris A, Aeschlimann S, et al. Increasing the Templating Effect on a Bulk Insulator Surface: From a Kinetically Trapped to a Thermodynamically More Stable Structure. Journal of Physical Chemistry C. 2016;120(31):17546-17554.Molecular self-assembly, governed by the subtle balance between intermolecular and molecule surface interactions, is generally associated with the thermodynamic ground state, while the competition between kinetics and thermodynamics during its formation is often neglected. Here, we present a simple model system of a benzoic acid derivative on a bulk insulator surface. Combining high-resolution noncontact atomic force microscopy experiments and density functional theory, we characterize the structure and the thermodynamic stability of a set of temperature-dependent molecular phases formed by 2,5-dihydroxybenzoic acid molecules, self-assembled on the insulating calcite (10.4) surface. We demonstrate that a striped phase forms before the thermodynamically favored dense phase, indicating a kinetically trapped state. Our theoretical analysis elucidates that this striped-to-dense phase transition is associated with a distinct change in the chemical interactions involved in the two phases. The striped phase is characterized by a balance between molecule molecule and molecule substrate interactions, reminiscent of the molecular bulk. In contrast, the dense phase is formed by upright standing molecules that strongly anchor to the surface with a comparatively little influence of the intermolecular interactions, in the latter case the substrate acts as a template for the molecular structure. The kinetic trapping stems from a relatively strong intermolecular interaction between molecules in the striped phase that need to be broken before the substrate-templated dense phase can be formed. Thus, our results provide molecular level insights into two qualitatively different bonding motifs of a simple organic molecule on a bulk insulator surface. This understanding is mandatory for obtaining predictive power in the rational design of molecular structures on insulating surfaces