For our simulations, a series of electrified Pt(111)|water interface models have been created at different free charge densities; for charge neutrality of the double layer, σ Pt 1L is compensated by counter ions. A detailed explanation of the methodological setup is given in the Supporting Information (SI), also describing the nature of the charges as well as their location and present counterions. Furthermore, due to the charge equilibration approach in ReaxFF the platinum atomic charges are not fixed but allowed to fluctuate (dynamically determined by the local environment), the only restriction being the imposed total charge of the slab. The resulting charge on the surface layer atoms yields a specific surface charge density corresponding to a certain electrode potential (see Fig. of the SI). Depending on the electrode potential, the charge distribution within the platinum slab differs, though showing some commonalities: As can be seen in Fig. (b), the main charge is located at the surface layers of the symmetrical platinum slab (denoted Pt 1L ). The subsequent layers show a slight Friedel oscillation, until the atomic charges deviate only marginally from the mean bulk charge. To account for charge compensation of the platinum surface, counter ions, i.e. K + and F -, are introduced to the system and are located at the outer Helmholtz plane as well as in the subsequent diffuse layer, see Fig. . This approach realizes a self-consistent description of the entire electrochemical interface and thus promises a more realistic ion distribution as compared to homogeneous background charges, the usage of an effective screening medium or Gaussian charge sheets as often employed in AIMD simulations. As ReaxFF enables simulations in the nanosecond timescale, the interface including the ion distribution is sufficiently equilibrated, also enabling an extensive and representative sampling of the phase-space. The σ Pt 1L (see Fig. its orientational ordering in the interface may be of relevance here. In the following, we self-consistently investigate these characteristica in detail.