Hidden Beneath the Surface: Origin of the Observed Enantioselective Adsorption on PdGa(111).

We unravel the origin of the recently observed striking enantioselectivity of the PdGa(l1l) surface with respect to the adsorption of a small organic molecule, 9- ethynylphenanthrene, using first-principles calculations. It turns out that the key ingredient to understand the experimental evidence is...

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Bibliographic Details
Published in:Journal of the American Chemical Society Vol. 140; no. 4; pp. 1401 - 1409
Main Authors: Yakutovich, Aliaksandr V., Hoja, Johannes, Passerone, Daniele, Tkatchenko, Alexandre, Pignedoli, Carlo A.
Format: Article
Published: American Chemical Society 1/31/2018
Subjects:
Online Access:View this record in EBSCOhost
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      dt: 1/31/2018
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        10.1021/jacs.7b10980
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        atl: Hidden Beneath the Surface: Origin of the Observed Enantioselective Adsorption on PdGa(111).
      aug:
        au:
          Yakutovich, Aliaksandr V.
          Hoja, Johannes
          Passerone, Daniele
          Tkatchenko, Alexandre
          Pignedoli, Carlo A.
        affil:
          Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Nanoscale Materials Science, CH-8600 Dübendorf, Switzerland
          Physics and Materials Science Research Unit, University of Luxembourg, 1511 Luxembourg, Luxembourg
      su:
        Palladium
        Enantioselective catalysis
        Adsorption (Chemistry)
        Van der Waals forces
        Density functionals
      sug:
        subj:
          Palladium
          Enantioselective catalysis
          Adsorption (Chemistry)
          Van der Waals forces
          Density functionals
      ab: We unravel the origin of the recently observed striking enantioselectivity of the PdGa(l1l) surface with respect to the adsorption of a small organic molecule, 9- ethynylphenanthrene, using first-principles calculations. It turns out that the key ingredient to understand the experimental evidence is the appropriate description of van der Waals interactions beyond the widely employed atomic pairwise approximation. A recently developed van der Waals-inclusive density functional method, which encompasses dielectric screening effects, reveals the origin of the experimentally observed enantioselectivity and provides conclusive evidence of chiral recognition on a bimetallic surface driven by dispersion interactions. The incorporation of dielectric screening leads to a renormalization of the dispersion interaction range, allowing for the appropriate weighting of the molecule -- substrate interactions at intermediate distances between 2.5 and 5 Á Our findings have implications for the structure and stability of complex organic/inorganic systems where dielectric screening effects are expected to be of general importance.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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