SKM 2023 – wissenschaftliches Programm
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O: Fachverband Oberflächenphysik
O 86: Solid-Liquid Interfaces II: Reactions and Electrochemistry I
O 86.1: Vortrag
Donnerstag, 30. März 2023, 15:00–15:15, TRE Phy
Enter the Void: Cavity Formation at Metal-Water Interfaces — •Thorben Eggert1,2, Nicolas G. Hörmann1, and Karsten Reuter1 — 1Fritz-Haber-Institut der MPG, Berlin, Germany — 2Technical University of Munich, Munich, Germany
Cavity formation is an important concept when rationalizing the solvation of ions. However, most studies only analyze cavities in bulk liquids, omitting that their properties may change dramatically at solid-liquid interfaces.
Here, we study cavities at interfaces, particularly their free energy of formation based on classical molecular dynamics simulations. Specifically, we use a particle insertion approach, as well as thermodynamical integration via the Multistate Bennett Acceptance Ratio. We demonstrate that cavity formation at interfaces depends on the substrate material, which can be rationalized by the strength of the substrate-water interaction. Furthermore, we observe deviations from the bulk behavior in the second solvation layer, which underlines the importance of the substrate-specific interfacial water structure. Finally, we validate our findings with ab initio molecular dynamics simulations.
These results allow a quantification of the competitive nature of adsorption processes at solid-liquid interfaces. Ultimately, they could improve implicit solvation models, which typically neglect substrate-specificity.