Molecular dynamics simulation studies of the limiting conductances of MgCl2 and CaCl2 in supercritical water using SPC/E model for water

We report results of molecular dynamics (MD) simulations of the limiting conductances of MgCl2 and CaCl2 in supercritical water as a function of water density using the SPC/E model for water. The limiting conductances of Mg2+, Ca2+ and Cl- over the whole range of water density considered exhibits a linear dependence of the limiting conductance on the water density. In the cases of Mg2+ and Ca2+ , a solventberg picture for the behavior of small divalent cation emerges from our studies. From the view of the solventberg picture, the ion and its shell moving together as an entity interacts with the second hydration shell water molecules, and its mobility is restricted mostly by the number of the second hydration shell water which is proportional to the water density of the whole system. In the case of Cl- , the range of water density considered in this study belongs to the higher-density region (above 0.45 g/cm(3) ) in which the effect of the number of hydration water molecules around ions dominated. As the water density increases, the water molecules of the first hydration shell restrict the mobility of Cl- and the limiting conductance of Cl- decreases nearly linearly. Significant different dependence on the water density is observed between the calculated limiting conductances of MgCl2 and CaCl2 at 673 K and the experimental results over the water density of 0.60-0.90 g/cm(3) . Possible limitation of the extended simple point charge (SPC/E) model with regard to this difference should be pointed out and the use of a more precise model like the revised polarizable (RPOL) model is indispensable for a further MD study to gain a complete picture of the chemical circumstance around the ions.