An atomic description of water dynamics and electrochemical properties at electrode-electrolyte interfaces is presented using molecular dynamics with the third generation of the charge-optimized many-body (COMB3) potential framework. Externally applied potentials in electrochemical applications were simulated by offsetting electronegativity on electrode atoms. This approach is incorporated into the variable charge scheme within COMB3 and is used to investigate electrochemical systems consisting of two Cu electrodes and a water electrolyte with varying concentrations of hydroxyls (OH-) and protons (H+). The interactions between the electronegativity offset method and the charge equilibration method in a variable charge scheme are analyzed. In addition, a charge equilibration method for electrochemical applications is proposed, where the externally applied potentials are treated by the electronegativity offset on the electrodes thus enforcing charge neutrality on the electrolyte. This method is able to qualitatively capture the relevant electrochemistry and predict consistently correct voltages with precalibration.