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O: Fachverband Oberflächenphysik

O 96: Solid-Liquid Interfaces IV: Reactions and Electrochemistry

O 96.9: Talk

Thursday, March 21, 2024, 17:15–17:30, TC 006

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

Computationally, the predictive-quality modeling of cyclic voltammograms (CVs) is complicated by the need to accurately account for the interactions and reactive chemistry at the liquid electrolyte/solid electrode interface, as well as for the electrostatic interactions of the diffuse double layer at applied potential conditions [1]. For sufficiently small scan rates, ab initio thermodynamics approaches help to meet these challenges.
Here, we compare different approximations commonly employed in such approaches [1]. Using the well-studied model system of Ag(100) in a Br-containing electrolyte as a show case, we analyze the influence of statistical sampling of the adlayer, how implicit solvent models affect the surface energetics, and the benefits of augmenting traditional zero-field calculations - aka the computational hydrogen electrode (CHE) - with capacitive double layer energetics (CHE+DL) [2]. Finally, we illustrate the possibility to expand our methodology to more complex systems by examining the CVs of Cu(100) electrodes in alkaline, I-containing electrolytes.
[1] N. Bergmann, N.G. Hörmann, and K. Reuter, J. Chem. Theory Comput. (in press) DOI:10.1021/acs.jctc.3c00957.
[2] N.G. Hörmann and K. Reuter, J. Chem. Theory Comput. 17, 1782 (2021).

Keywords: Ab Initio; DFT; Cyclic Voltammogram; Monte Carlo