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Article Citation - WoS: 14Dissociative Adsorption of Water at (211) Stepped Metallic Surfaces by First-Principles Simulations(Amer Chemical Soc, 2017) Pekoz, Rengin; Donadio, DavideSteps at high-index metallic surfaces display higher chemical reactivity than close-packed surfaces and may give rise to selective adsorption and partial dissociation of water. Inspired by differential desorption experiments, we have studied the adsorption and dissociation of water clusters and one-dimensional wires on Pt(211) by density functional theory and molecular dynamics simulations. These calculations reveal that water at the step edges of Pt(211) adsorbs more weakly than at Pt(221), but partial dissociation of adsorbed water clusters is energetically competitive. We observe that the one-dimensional structure proposed experimentally can be realized only by partially dissociated water wires. In addition, weaker adsorption allows the formation of structures in which a number of water molecules detach from the step and form weak hydrogen bonds with the terrace. This study is further extended to the energetics of small water clusters on (211) surfaces of Ir, Rh, and Pd.Article Citation - WoS: 2Citation - Scopus: 3Selective Adsorption of a Supramolecular Structure on Flat and Stepped Gold Surfaces(Elsevier, 2018) Pekoz, Rengin; Donadio, DavideHalogenated aromatic molecules assemble on surfaces forming both hydrogen and halogen bonds. Even though these systems have been intensively studied on flat metal surfaces, high-index vicinal surfaces remain challenging, as they may induce complex adsorbate structures. The adsorption of 2,6-dibromoanthraquinone (2,6-DBAQ) on flat and stepped gold surfaces is studied by means of van der Waals corrected density functional theory. Equilibrium geometries and corresponding adsorption energies are systematically investigated for various different adsorption configurations. It is shown that bridge sites and step edges are the preferred adsorption sites for single molecules on flat and stepped surfaces, respectively. The role of van der Waals interactions, halogen bonds and hydrogen bonds are explored for a monolayer coverage of 2,6-DBAQ molecules, revealing that molecular flexibility and intermolecular interactions stabilize two-dimensional networks on both flat and stepped surfaces. Our results provide a rationale for experimental observation of molecular carpeting on high-index vicinal surfaces of transition metals. (C) 2017 Elsevier B.V. All rights reserved.
