Increasing the templating effect on a bulk insulator surface: from a kinetically trapped to a thermodynamically more stable structure

Paris, Chiara, Floris, Andrea, Aeschlimann, Simon , Kittelmann, Markus, Kling, Felix, Bechstein, Ralf, Kuhnle, Angelika and Kantorovich, Lev (2016) Increasing the templating effect on a bulk insulator surface: from a kinetically trapped to a thermodynamically more stable structure. Journal of Physical Chemistry C, 120 (31). pp. 17546-17554. ISSN 1932-7447

Full content URL: https://doi.org/10.1021/acs.jpcc.6b05402

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Abstract

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, i.e., 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. © 2016 American Chemical Society.

Keywords:Atomic force microscopy, Benzoic acid, Chemical analysis, Chemical bonds, Density functional theory, Ground state, Insulating materials, Kinetics, Molecular structure, Molecules, Self assembly, Thermodynamic stability, Thermodynamics, 2 ,5-dihydroxybenzoic acids, Benzoic acid derivatives, Intermolecular interactions, Kinetics and thermodynamics, Molecular self assembly, Molecular-level insights, Molecule substrate interactions, Noncontact atomic force microscopy, Phase transitions, NotOAChecked
Subjects:F Physical Sciences > F170 Physical Chemistry
Divisions:College of Science > School of Mathematics and Physics
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ID Code:23871
Deposited On:26 Aug 2016 10:02

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