Based on constant Fermi-level molecular dynamics and a proper alignment scheme, we perform simulations of the Pt(111)/water interface under variable bias potential referenced to the standard hydrogen electrode (SHE). Our scheme yields a potential of zero charge µ pzc of ∼ 0.22 eV relative to the SHE and a double layer capacitance C dl of ≃ 19 µFcm −2 , in excellent agreement with experimental measurements. In addition, we study the structural reorganization of the electrical double layer for bias potentials ranging from −0.92 eV to +0.44 eV and find that Odown configurations, which are dominant at potentials above the pzc, reorient to favor Hdown configurations as the measured potential becomes negative. Our modeling scheme allows one to not only access atomic-scale processes at metal/water interfaces, but also to quantitatively estimate macroscopic electrochemical quantities.