SKM 2023 – wissenschaftliches Programm

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O: Fachverband Oberflächenphysik

O 86: Solid-Liquid Interfaces II: Reactions and Electrochemistry I

O 86.8: Vortrag

Donnerstag, 30. März 2023, 17:00–17:15, TRE Phy

Thermodynamic Cyclic Voltammograms from First Principles — •Nicolas Bergmann, Nicolas G. Hörmann, and Karsten Reuter — Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin, Germany

Cyclic voltammograms (CVs) are a central experimental tool for assessing the structure and activity of electrochemical interfaces. Computationally, a predictive-quality modeling of CVs is challenging due to the entangled need to accurately account for the interactions and reactive chemistry at the liquid electrolyte/solid electrode interface as well as for the applied potential [1]. For sufficiently small scan rates, thermodynamic approaches help to meet these challenges.

Here, we compare different options to derive thermodynamic CVs consistently and at low computational cost, using the well-studied model system of Ag(100) in a Br-containing electrolyte as a test case. We present our generalized ansatz to derive continuous expressions within a mean-field (MF) model, using non-parametric Gaussian process regression. We also shine light on the inherent accuracy limitations of MF theory, by comparing it to CVs from grand-canonical lattice Monte Carlo simulations. Finally, we show how augmenting traditional zero-field calculations (computational hydrogen electrode, CHE) with capacitive double layer energetics (CHE+DL) [1] within an implicit solvent model influences the theoretical results.

[1] N.G. Hörmann et al., J. Chem. Theory Comput. 2021, 17, 1782