Hydrogen-Bonded Cyclic Water Clusters Nucleated on an Oxide Surface.

We report the observation and molecular-scale scanning probe electronic structure (dl/dV) mapping of hydrogen-bonded cyclic water clusters nucleated on an oxide surface. The measurements are made on a new type of cyclic water cluster that is characterized by simultaneous and cooperative bonding inte...

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Publicado en:Journal of the American Chemical Society Vol. 136; no. 38; pp. 13283 - 13289
Autores principales: Kronawitter, Coleman X., Riplinger, Christoph, Xiaobe He, Zahl, Percy, Carter, Emily A., Sutter, Peter, Koel, Bruce E.
Formato: Artículo
Publicado: American Chemical Society 9/24/2014
Materias:
Acceso en línea:Ver este registro en EBSCOhost
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        10.1021/ja5056214
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        atl: Hydrogen-Bonded Cyclic Water Clusters Nucleated on an Oxide Surface.
      aug:
        au:
          Kronawitter, Coleman X.
          Riplinger, Christoph
          Xiaobe He
          Zahl, Percy
          Carter, Emily A.
          Sutter, Peter
          Koel, Bruce E.
        affil:
          Department of Chemical & Biological Engineering, Princeton University, Princeton, New Jersey, United States
          Department of Mechanical & Aerospace Engineering, Program in Applied & Computational Mathematics, Princeton University, Princeton, New Jersey, United States
          Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York, United States
          Andlinger Center for Energy & the Environment, Princeton University, Princeton, New Jersey, United States
      su:
        Hydrogen bonding
        Crystal chemical bonds
        Electronic structure
        Density functional theory
        Stoichiometry
      sug:
        subj:
          Hydrogen bonding
          Crystal chemical bonds
          Electronic structure
          Density functional theory
          Stoichiometry
      ab: We report the observation and molecular-scale scanning probe electronic structure (dl/dV) mapping of hydrogen-bonded cyclic water clusters nucleated on an oxide surface. The measurements are made on a new type of cyclic water cluster that is characterized by simultaneous and cooperative bonding interactions among molecules as well as with both metal and oxygen sites of an oxide surface. Density functional theory + U + D calculations confirm the stability of these clusters and are used to discuss other potential water-oxide bonding scenarios. The calculations show that the spatial distributions of electronic states in the system are similar in character to those of the lowest unoccupied molecular orbitals of hydrogen-bonded water molecules. On the partially oxidized Cu(111) investigated here, experiment and theory together suggest that Cu vacancies in the growing islands of cuprous oxide inhibit water adsorption in the centers of the islands (which have reached thermodynamic equilibrium). A stoichiometric, less stable cuprous oxide likely exists at island edges (the growth front) and selectively binds these water clusters.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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