Density functional theory-based electrochemical models for the oxygen reduction reaction: Comparison of modeling approaches for electric field and solvent effects

Kuan Yu Yeh, Michael John Janik

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A series of density functional theory (DFT) based electrochemical models are applied to systematically examine the effect of solvent, local electric field, and electrode potential on oxygen reduction reaction (ORR) kinetics. Specifically, the key elementary reaction steps of molecular oxygen dissociation, molecular oxygen protonation, and reduction of a hydroxyl adsorbate to water over the Pt(111) surface were considered. The local electric field has slight influence on reaction energetics at the vacuum interface. Solvent molecules stabilize surface adsorbates, assisting oxygen reduction. A collective solvation-potential coupled effect is identified by including long range solvent-solvent interactions in the DFT model. The dominant path of the ORR reaction varies with electrode potential and among the modeling approaches considered. The potential dependent reaction path determined from the solvated model qualitatively agrees with experiment ORR kinetics.

Original languageEnglish (US)
Pages (from-to)3399-3408
Number of pages10
JournalJournal of Computational Chemistry
Issue number16
StatePublished - Dec 1 2011


All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Computational Mathematics

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