To the author's knowledge, this shift to a dominating H-down configuration in the surface oxidation potential region is so far undocumented. A detailed discussion of the structure of the water layer as well as the occurrence of ordered patterns will be presented together with the spatially-resolved entropy behavior later. Near the assumed location of the potential of zero charge (pzc, ∼0.3 V), both H-up and H-down orientations of the interfacial water molecules (e.g. H 2 O within 3.5 Å distance to the Pt surface) are observed. In Fig. , this is represented by a comparable proportion of both configurations. Up to 0.5 V, the H-up orientation is distinctly preferred, in line with AIMD studies. This indicates a strong correlation between the water orientation and the free charge density, as with a more positively charged surface the hydrogen atoms tend to point away from the surface. and O * ) promotes the reorientation of interfacial water molecules to pointing their positive charges on the hydrogen atoms towards the surface. This is visualized in Fig. , where the H-down configuration is observed for up to 66 % of the interfacial water molecules between 0.9 V and 1.0 V. The median of the angle ψ between the water bisector vector and the surface supports additionally our observation of the preference of the H-down configuration with increasing potential: ψ median is changing from 61.7 • at 0.44 V to its maximum value of 105.2 • at 1.0 V. This reorientation is however restricted to the water molecules within a few Ångströms distance to the Pt(111) surface. Further away from the platinum surface, the water molecules shows random orientations and are only locally affected by charged ions.