Potential‐Dependent Pt(111)/Water Interface: Tackling the Challenge of a Consistent Treatment of Electrochemical Interfaces**

The interface between an electrode and an electrolyte is where electrochemical processes take place for countless technologically important applications. Despite its high relevance and intense efforts to elucidate it, a description of the interfacial structure and, in particular, the dynamics of the electric double layer at the atomic level is still lacking. Here we present reactive force-field molecular dynamics simulations of electrified Pt(111)/water interfaces, shedding light on the orientation of water molecules in the vicinity of the Pt(111) surface, taking into account the influence of potential, adsorbates, and ions simultaneously. We obtain a shift in the preferred orientation of water in the surface oxidation potential region, which breaks with the previously proclaimed strict correlation to the free charge density. Moreover, the characterization is complemented by course of the entropy and the intermolecular ordering in the interfacial region complements the characterization. Our work contributes to the ongoing process of understanding electric double layers and, in particular, the structure of the electrified Pt(111)/water interface, and aims to provide insights into the electrochemical processes occurring there.