On the halide hydration study: Development of first-principles halide ion-water interaction potential based on a polarizable model

Abstract

The development of first-principles halide-water interaction potentials for fluoride and iodide anions is presented. The model adopted is the mobile charge densities in harmonic oscillator that allows for a flexible and polarizable character of the interacting particles. The set of points of the quantum mechanical potential energy surfaces are calculated up to the MP2 level. The nonadditive many-body contributions were included explicitly at the three-body terms. Structural and energetic properties of the [ X(H2O)n ]- clusters (n=1 – 6) are studied with the new interaction potentials developed. Halide aqueous solutions are also studied by means of Monte Carlo simulations. The agreement between experimental and our predicted estimations shows the good behavior of the proposed potentials. The developed potentials are able to properly describe both the microsolvation of clusters in gas phase and their hydration in aqueous solutions. The different nature of the interactions among F-, Br-, I- and water appears in the set of studied properties, thus giving a gradual change in the behavior along the group.