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Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics
Published on: April 12, 2019
Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the
Egill Skúlason1, Gustav S Karlberg, Jan Rossmeisl
1Center for Atomic-scale Materials Design, Department of Physics, Building 307, NanoDTU, Technical University of Denmark, DK-2800, Lyngby, Denmark.
Abstract:
We present results of density functional theory calculations on a Pt(111) slab with a bilayer of water, solvated protons in the water layer, and excess electrons in the metal surface. In this way we model the electrochemical double layer at a platinum electrode. By varying the number of protons/electrons in the double layer we investigate the system as a function of the electrode potential. We study the elementary processes involved in the hydrogen evolution reaction, 2(H(+) + e(-)) --> H(2), and determine the activation energy and predominant reaction mechanism as a function of electrode potential. We confirm by explicit calculations the notion that the variation of the activation barrier with potential can be viewed as a manifestation of the Brønsted-Evans-Polanyi-type relationship between activation energy and reaction energy found throughout surface chemistry.
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