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Adsorption of successive layers of H2 molecules on a model copper surface: performances of second- to fifth-rung exchange-correlation functionals

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Abstract

The interaction of H2 molecules with a Cu(100) metallic surface has been investigated by DFT approaches using a (H2) n Cu13 cluster model. Nine exchange-correlation functionals, belonging to the generalized gradient approximations (GGA), meta GGA (mGGA), hybrid Kohn–Sham/Hartree–Fock models, either based on GGAs or mGGAs, range-separated hybrids, and double-hybrid families, have been tested on the chemisorption and physisorption processes involving one or two H2 layers. The addition of an empirical correction for dispersion has also been tested for some of these functionals. The calculated energies and structural parameters were compared to sophisticated multi reference configuration interaction including Davidson’s correction for quadruple excitations (MRCI + Q). Our results show that among the nine considered exchange-correlation functionals, none can accurately reproduce all processes involved in the successive layers adsorption. Although an hybrid based on a mGGA such as M06-2X can quantitatively describe both the physisorption step and dissociation barriers involved in the adsorption of the first H2, it fails to reproduce its chemisorption. On the other hand, significant discrepancies with the reference post-HF data are obtained for the description of the second layer interaction, no matter which functional is considered, outlining the need of improvement and/or development of exchange-correlation functionals suitable for complex systems such as H2/H2Cu.

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Authors and Affiliations

  1. Laboratoire Modélisation et Simulation Multi Echelle, UMR 8208-CNRS, Université Paris-Est, 5 boulevard Descartes, Marne-la-Vallée, 77454, France

    Géraldine Cilpa & Gilberte Chambaud

  2. Laboratoire d’Electrochimie, Chimie des Interfaces et Modélisation pour l’Energie, UMR CNRS 7575, ENSCP—Chimie Paristech, 11 rue P. et M. Curie, Paris Cedex 05, 75231, France

    Jonathan Colin, Frédéric Labat & Carlo Adamo

  3. Institut Universitaire de France, 103 Boulevard Saint Michel, Paris, 75005, France

    Carlo Adamo

Authors
  1. Géraldine Cilpa
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  2. Jonathan Colin
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  3. Frédéric Labat
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  4. Carlo Adamo
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  5. Gilberte Chambaud
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Correspondence to Frédéric Labat.

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Dedicated to Professor Vincenzo Barone and published as part of the special collection of articles celebrating his 60th birthday.

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Cilpa, G., Colin, J., Labat, F. et al. Adsorption of successive layers of H2 molecules on a model copper surface: performances of second- to fifth-rung exchange-correlation functionals. Theor Chem Acc 131, 1189 (2012). https://doi.org/10.1007/s00214-012-1189-8

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