Role of local order in anomalous ion diffusion: Interrogation through tetrahedral entropy of aqueous solvation shells

Small rigid ions perturb the water structure around them significantly. At constant viscosity, alkali cations (Li⁺, Na⁺, and so on) exhibit an anomalous non-monotonic dependence of diffusivity on ion-size, in stark violation of the Stokes-Einstein expression. Although this is a well-known problem, we find that an entropic view of the problem can be developed, which provides valuable insight. The local entropy experienced by the solute ion is relevant here, which leads to the connection with local viscosity, discussed earlier by many. Due to the strong interactions with ions, the translational and rotational entropy of solvation water decreases sharply; however, an opposite effect comes from the disruption of the tetrahedral network structure of water near the charges. We compute the tetrahedral order of water molecules (q_tet) around the ion and suitably defined tetrahedral entropy [S(q_tet)] that is a contribution to the excess entropy of the system. Our results reveal that although the structural properties of the second shell become nearly identical to the bulk, S(q_tet) of the second shell is found to play an important role in giving rise to the non-monotonic ion-size dependence. The detailed study of the static and dynamic fluctuations in q_tet and the number of hydration water molecules provides interesting insights into correlation between the structure and dynamics; the smallest static fluctuation of q_tet for the first hydration shell water molecules of Li⁺ is indicative of the iceberg picture. The study of fluctuation properties of q_tet and the coordination number also reveals the role of the second hydration layer and could explain the anomalous behavior of the Rb⁺ ion.