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Mechanisms of Covalent Dimerization on a Bulk Insulating Surface

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School of Physics and Technology, Wuhan University, Wuhan 430072, China
Institute of Physical Chemistry, University of Mainz, 55099 Mainz, Germany
§ Department of Physics, King’s College London, Strand, London WC2R 2LS, United Kingdom
School of Mathematics and Physics, University of Lincoln, Brayford Pool, LN6 7TS Lincoln, United Kingdom
*Phone: +44 1522 83 5884. E-mail: [email protected]
*Phone: +44 020 7848 2160. E-mail: [email protected]
*Phone: +86 158 7135 1027. E-mail: [email protected]
Cite this: J. Phys. Chem. C 2017, 121, 18, 10053–10062
Publication Date (Web):April 12, 2017
Copyright © 2017 American Chemical Society

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    Combining density functional theory and high-resolution NC-AFM experiments, we have studied the on-surface reaction mechanisms responsible for the covalent dimerization of 4-iodobenzoic acid (IBA) organic molecules on the calcite (10.4) insulating surface. When annealed at 580 K, the molecules assemble in one-dimensional chains of covalently bound dimers. The chains have a unique orientation and result from a complex set of processes, including a nominally rather costly double dehalogenation reaction followed by dimerization. First, focusing on the latter two processes and using the nudged elastic band method, we analyze a number of possible mechanisms involving one and two molecules, and we isolate the key aspects facilitating the reaction on calcite. Second, we find that the insulating surface plays an active role as a catalyst by identifying two relevant processes: one exhibiting an intermediate state of chemisorbed molecules after independent dehalogenations and a second, highly nontrivial exothermic reaction channel in which two iodine atoms “cooperate” to minimize the cost of their individual detachment from the molecules. Both processes have dramatically reduced energy barriers compared to all other mechanisms analyzed. The knowledge of the formation mechanisms of a covalent assembly on insulators represents an important step toward the realization and control of structures that combine the robustness of covalent architectures with their electronic decoupling from the insulating substrate. This step has potentially important technological applications in nano- and molecular electronics.

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpcc.7b02687.

    • (1) IBA molecule in the gas phase: structure and dehalogenation processes. (2) IBA adsorption geometries on calcite (10.4). (3) Dehalogenated IBA molecule with a iodine atom on calcite (10.4). (4) Iodine atom and I2 molecule adsorption geometries on calcite (10.4). (5) H-bond energy. (6) IBA dimer adsorption geometries on calcite (10.4). (7) Single-molecule dehalogenation on calcite (10.4). (8) Dehalogenation process with I2 molecule formation. (9) Double dehalogenation–dimerization process in the gas phase. (10) Two nonbonded IBA molecules adsorption geometries on calcite (10.4). (11) Entropy contribution of a gas of I2 molecules to the free energy. (12) Spin-resolved versus spin-unresolved energy barriers in processes including the substrate. (13) Stable configurations of two hydrogen atoms in the presence of a calcite (10.4) surface (PDF)

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