The growing interest in the effects of external electric fields on reactive processes requires predictive methods that can reach longer length and time scales than quantum mechanical simulations. Recently, many studies have included electric fields in ReaxFF, a widely used reactive molecular dynamics method. In the case of modeling an external electric field, the charge distribution method used in ReaxFF is critical. The most common charge distribution method used in previous studies of electric fields is the charge equilibration (QEq) method, which assumes that the system is a contiguous conductor and that charge transfer can occur across any distance. In contrast, many systems of interest are insulators or semiconductors, and long-distance charge transfer should not occur in response to a small difference in potential. This study focuses on the limitations of the QEq method in the context of water in an external electric field. We demonstrate that QEq can predict unphysical charge distributions and exhibits properties that do not converge as a function of system size. Furthermore, we show that electric fields within the recently developed atom-condensed Kohn-Sham density functional theory (DFT) approximated to the second-order (ACKS2) approach address the major limitations of electric fields in QEq. With ACKS2, we observe more physical charge distributions and properties that converge as a function of system size. We do not suggest that ACKS2 is perfect in all circumstances but rather show specific cases where it addresses the major shortcomings of QEq in the context of an external electric field.