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O: Fachverband Oberflächenphysik
O 96: Solid-Liquid Interfaces IV: Reactions and Electrochemistry
O 96.5: Talk
Thursday, March 21, 2024, 16:15–16:30, TC 006
Potentially Uncontrolled Barrier Calculations for Electrocatalysis — •Simeon D. Beinlich1,2, Georg Kastlunger3, Karsten Reuter1,2, and Nicolas G. Hörmann1 — 1Fritz-Haber-Institut der MPG, Berlin — 2Technische Universität München — 3Technical University of Denmark, Kongens Lyngby, Denmark
Does computing electrochemical barriers necessarily require the use of a potentiostat? Here, we present a novel set of potentiostat-free methods for computing grand canonical activation barriers at constant potential from common canonical DFT calculations [1]. Making most efficient use of the underlying DFT data, these methods can, by construction, re-create potentiostat-based results. Moreover, they offer several systematic approximations that cover the potential-induced electronic and geometric responses, while only requiring a single transition state search at the point of zero charge, i.e. at zero excess charge.
Besides offering new pathways for efficiently calculating electrochemical activation barriers, our analysis highlights the importance of including geometric effects and more generally sheds light on the similarities and dissimilarities between a canonical and a grand canonical treatment of electrochemical interfaces. [1] S.D. Beinlich et al., J. Chem. Theory Comput., https://doi.org/10.1021/acs.jctc.3c00836
Keywords: electrocatalysis; electrochemical barriers; constant potential; grand canonical calculations; geometric effects