Modeling the electrified solid–liquid interface

https://doi.org/10.1016/j.cplett.2008.10.024Get rights and content

Abstract

A detailed atomistic model based on density functional theory calculations is presented of the charged solid–electrolyte interface. Having protons solvated in a water bilayer outside a Pt(1 1 1) slab with excess electrons, we show how the interface capacitance is well described and how the work function can be related directly to the potential scale of the normal hydrogen electrode. We also show how finite-size effects in common periodic slab-type calculations can be avoided in calculations of activation energies and reaction energies for charge transfer reactions, where we use the Heyrovsky reaction for hydrogen oxidation over a Pt(1 1 1) electrode as an example.

Graphical abstract

We present an atomistic model of the charged solid–electrolyte interface based on DFT where finite-size effects are avoided.

  1. Download : Download full-size image

Section snippets

Acknowledgments

CAMD is funded by the Lundbeck foundation. This work was supported by the Danish Center for Scientific Computing through grant no. HDW-1103-06 and by the EU through the FC-Anode network, STREP no. NMP-2007-032175.

References (34)

  • T.E. Shubina et al.

    Electrochem. Commun.

    (2006)
  • A. Roudgar et al.

    Chem. Phys. Lett.

    (2005)
  • Y. Okamoto et al.

    Chem. Phys. Lett.

    (2003)
  • O. Sugino et al.

    Surf. Sci.

    (2007)
  • E.R. Kötz et al.

    J. Electroanal. Chem.

    (1986)
  • T. Pajkossy et al.

    Electrochim. Acta

    (2001)
  • N. Agmon

    Chem. Phys. Lett.

    (1995)
  • O. Pecina et al.

    Chem. Phys.

    (1998)
  • H.L.F. von Helmholtz

    Ann. Phys.

    (1853)
  • G. Gouy

    Compt. Rend.

    (1910)
  • D.L. Chapman

    Philos. Mag.

    (1913)
  • O. Stern

    Z. Electrochem.

    (1924)
  • D.C. Grahame

    Chem. Rev.

    (1947)
  • A.B. Anderson et al.

    J. Am. Chem. Soc.

    (1999)
  • A.B. Anderson et al.

    J. Electrochem. Soc.

    (2000)
  • J. Greeley et al.

    J. Am. Chem. Soc.

    (2004)
  • J.K. Nørskov et al.

    J. Phys. Chem. B

    (2004)
  • Cited by (0)

    View full text