Ab Initio Molecular Dynamics Simulation of the Phosphate Ion in Water: Insights into Solvation Shell Structure, Dynamics, and Kosmotropic Activity

Abstract

The structure and dynamics of solvation shells of the phosphate ion in deuterated water are studied by means of Born–Oppenheimer molecular dynamics simulation. The total number of molecules in the first and second solvation shells is found to be close to the effective hydration number reported experimentally. The OD bonds that are hydrogen bonded to the phosphate ion are found to be red shifted as compared to bulk water, which is consistent with experimental results. However, the two OD bonds of the same water molecule in the first hydration shell are found to be vibrationally distinct, which can be attributed to different strengths of the ion–water and water–water hydrogen bonds near the ion. Also, the hydrogen bonds formed by the second solvation shell OD bonds are somewhat stronger than the bulk. This finding shows a long ranged effect of the phosphate ion on water and also gives insights into the water structure making property of this anion. The dynamics of water in the first solvation shell is found to be significantly slower than that of the bulk. We have investigated the origin of the orientational slowing down of the first solvation shell water molecules and made connections to similar results observed experimentally.