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Density functional theory‐based electrochemical models for the oxygen reduction reaction: Comparison of modeling approaches for electric field and solvent effects
Author(s) -
Yeh KuanYu,
Janik Michael J.
Publication year - 2011
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21919
Subject(s) - chemistry , solvation , density functional theory , dissociation (chemistry) , electrochemistry , solvent , elementary reaction , protonation , solvent effects , implicit solvation , electric field , oxygen , computational chemistry , chemical physics , kinetics , electrode , organic chemistry , ion , physics , quantum mechanics
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. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011