The study of ionic liquids that may be compatible with the type of radiation chemistry events occurring in nuclear separation processes is a topic of high current interest. In this article, we focus on two ionic liquids based on the benzylpyridinium cation. This cation has been proposed to be able to capture either an excess electron or hole without undergoing fast dissociation. Shkrob, Wishart, and collaborators (j. Phys. Chem. B 2013, 117 (46), 14385-14399) have indicated that the stabilization is likely in the form of dimers in solution with the excess electron localized on adjacent pyridinium rings and the excess hole localized on phenyl rings. Our first principles dynamical studies support these ideas but present a more nuanced view of the time-dependent behavior that is likely to occur at short time for systems at room temperature.