Vibrational recognition of adsorption sites for CO adsorbed on transition-metal surfaces

ORAL

Abstract

We have studied the vibrational properties of carbon monoxide adsorbed on transition-metal surfaces, using density-functional perturbation theory in the GGA-PBE approximation. The full dispersions for CO adsorbed on high-symmetry surface sites have been calculated, obtaining excellent agreement with spectroscopic measurements. This agreement in predicting absolute frequencies and frequency shifts as a function of the adsorption site is at variance with the poor performance of most exchange- correlation functionals in describing the energetics of adsorption. We provide a simple physical picture justifying this accuracy. These results open the possibility to directly connecting experimental vibrational spectra with the microscopic details of adsorption geometries.

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Authors

  • Ismaila Dabo

    • Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139

  • Cody Friesen

    • Department of Chemical and Materials Engineering, Arizona State University, Tempe, AZ 85287

  • Andrzej Wieckowski

    • Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL 61801

  • Nicola Marzari

    • Department of Materials Science and Engineering, MIT
    • DMSE, MIT, Cambridge, MA 02139
    • Department of Materials Science and Engineering, Massachusetts Institute of Technology
    • DMSE-MIT
    • Department of Materials Science and Engineering and Institute for Soldier Nanotechnologies, Massachusetts Institute of Technology
    • DMSE and ISN Massachusetts Institute of Technology
    • Materials Science and Engineering, MIT
    • Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139