In combination, these data indicate that the self-association of water in the polar core is a predominant factor behind the preferred eclipsed conformation of TODGA in polar conditions. An eclipsed conformation maximize hydrogen bonding with surface waters; "surface coverage" of the amphipile about the polar core leads to enhanced Lennard-Jones interactions between TODGA molecules, rather than increased Coulomb interactions that might be anticipated from TODGA-TODGA interactions facilitated through individual H 2 O bridging interactions between neighboring head-groups. This interpretation has been enabled by the MSM workflow which further points to the important utility of Markov State Modeling to understand the fundamental dynamics of microemulsions systems. This works demonstrates the utility of Markov state modeling to elucidate the conformational energy landscape of amphiphiles, the way in which this PEL is modulated by solvent interactions, and finally the impact this has upon amphiphile self-assembly.