To understand and control the behavior of electrochemical systems, including batteries and electrocatalysts, we seek molecular-level details of the charge transfer mechanisms at electrified interfaces. Recognizing some key limitations of standard equilibrium electronic structure methods to model materials and their interfaces, we propose applying charge constraints to effectively separate electronic and nuclear degrees of freedom, which are especially beneficial to the study of conversion electrodes, where electronic charge carriers are converted to much slower polarons within a material that is nonmetallic. We demonstrate the need for such an approach within the context of sulfur cathodes and the arrival of Li ions during discharge of a Li-S cell. The requirement that electronic degrees of freedom are arrested is justified by comparison with real-time evolution of the electronic structure. Long-lived metastable configurations provide plenty of time for nuclear dynamics and relaxation in response to the electrification of the interface, a process that would be completely missed without applying charge constraints. This approach will be vital to the study of dynamics at electrified interfaces which may be created deliberately, adding charge to the electrode, or spontaneously, due to finite temperature dynamics in the electrolyte.