Successful a Priori Modeling of CO Adsorption on Pt(111) Using Periodic Hybrid Density Functional Theory.

The adsorption of CO on the surface of metals such as Pt(111)is of great interest owing to the industrial importance of the catalytic oxidation of pollutant CO. To date, reliable high-level calculations of this process have not been possible, a situation often referred to as the ‘CO/Pt(111) puzzle’....

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Publicado en:Journal of the American Chemical Society Vol. 129; no. 34; pp. 10402 - 10408
Autores principales: Yun Wang, De Gironcoli, Stefano, Hush, Noel S., Reimers, Jeffrey R.
Formato: Artículo
Publicado: American Chemical Society 8/29/2007
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Acceso en línea:Ver este registro en EBSCOhost
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        10.1021/ja0712367
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        atl: Successful a Priori Modeling of CO Adsorption on Pt(111) Using Periodic Hybrid Density Functional Theory.
      aug:
        au:
          Yun Wang
          De Gironcoli, Stefano
          Hush, Noel S.
          Reimers, Jeffrey R.
        affil: Contribution from the School of Chemistry and School of Molecular and Microbial Biosciences, The Universily of Sydney, NSW 2006, Australia, and SJSSA-Scuola Internazionale Superiore di Studi Auanzati and CNR-INFM DEMOCRITOS National Simulation Center, 1-34014 Trieste, Italy
      su:
        Adsorption (Chemistry)
        Density functionals
        Oxidation
        Carbon monoxide
        Absorption
        Chemical engineering
      sug:
        subj:
          Adsorption (Chemistry)
          Density functionals
          Oxidation
          Carbon monoxide
          Absorption
          Chemical engineering
      ab: The adsorption of CO on the surface of metals such as Pt(111)is of great interest owing to the industrial importance of the catalytic oxidation of pollutant CO. To date, reliable high-level calculations of this process have not been possible, a situation often referred to as the ‘CO/Pt(111) puzzle’. Standard generalized-gradient-approximation density functional theory approaches fail to capture key details of the binding, such as the location of the adsorption site, while cluster approaches using alternative methods show some but insufficient improvement. Using a new computational methodology combining hybrid density functionals containing non-local Hartree–Fock exchange with periodic imaging plane-wave-based techniques, we demonstrate that key aspects of the adsorption of CO on Pt(111), including the identification of the absorption site and CO frequency change, can now be adequately modeled. The binding is dominated by both CO dative covalent bonding and metal-to-molecule r back-bonding, effects requiring realistic alignment of both the molecular HOMO and LUMO orbitals with respect to the metal Fermi energy.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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