Solvation of Mg2+ ions in methanol-water mixtures: Molecular dynamics simulation

Molecular dynamics simulations of MgCl2 solutions in methanol-water mixtures, over the whole range of the methanol mole fraction at room temperature have been performed. The methanol and water molecules have been modeled as flexible three-site bodies. Solvation of the magnesium ions has been discussed on the basis of the radial and angular distribution functions, the orientation of the solvent molecules and their geometrical arrangement in the coordination shells. Analysis of the H-bonds of the solvent molecules coordinated by Mg2+ has been based on a geometric criterion of the H-bond. Persistence of the primary and secondary shell has been estimated. In all studied solutions Mg2+ is six-coordinated and the solvent molecules form an octahedron. The antidipole orientation of the molecules favours the water molecules as H-donors in the first shell and the methanol molecules as H-acceptor in the second shell. Thus an excess of water and an excess of methanol has been observed in the first and the second shells of Mg2+. An exchange of the solvent molecules between the primary and secondary shells occur. The persistence of the second shell is longer than the shells of monovalent ions. (C) 2012 Elsevier B.V. All rights reserved.