Benzene and Pyridine on Silicon (001): A Trial Ground for Long Range Corrections in Density Functional Theory

Publication: Research - peer-reviewJournal article

DOI

  • Oliver Warschkow
    Oliver WarschkowSydney University, Sydney
  • J.M. Bennett
    J.M. BennettSydney University, Sydney
  • J. A. Miwa
  • G. P. Lopinski
    G. P. LopinskiNatl Res Council Canada, National Research Council Canada
  • F. Rosei
    F. RoseiUniv Quebec, University of Quebec, Geotop
  • D. R. McKenzie
    D. R. McKenzieSydney University, Sydney
  • Nigel A. Marks
    Nigel A. MarksCurtin University

The adsorption chemistry of benzene and pyridine on the silicon (001) surface is characterized by two prominent adsorbate configurations: a precursor structure bonded to a single Si Si dimer and a "tight-bridge" configuration that connects two adjacent dimers. We examine here the performance of 20 density functionals in predicting the relative stability of these two configurations. Discrepancies between the predicted and experimentally observed preferred structures highlight the importance of long-range exact-exchange terms in these adsorbate systems. These terms, however, tend to be detrimental to the prediction of adsorption and activation energies. We discuss this conundrum in terms of systematic exchange-correlation errors that scale with the number of molecule-surface bonds.

Original languageEnglish
JournalThe Journal of Physical Chemistry Part C: Nanomaterials, Interfaces and Hard Matter
Volume121
Issue number19
Pages (from-to)10484-10500
Number of pages17
ISSN1932-7447
DOIs
StatePublished - 18 May 2017

    Keywords

  • GENERALIZED-GRADIENT-APPROXIMATION, SCANNING-TUNNELING-MICROSCOPY, BINDING STATE CONVERSION, ELECTRONIC-STRUCTURE, DISPERSION CORRECTIONS, CORRELATION-ENERGY, SURFACE-CHEMISTRY, SI(100) SURFACE, ADSORPTION, ACCURACY

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