Parameterization of Halogens for the Density-Functional Tight-Binding Description of Halide Hydration.

Abstract

Parameter sets of the self-consistent-charge density-functional tight-binding model with and without its third-order extension have been developed to describe the interatomic interactions of halogen elements (X = Cl, Br, I) with hydrogen and oxygen, with the ultimate goal of investigating halide hydration with this approach. The reliability and accuracy of the model with these newly developed parameters has been evaluated by comparing the structural, energetic, and vibrational properties of small molecules containing halogen atoms with those obtained by means of standard density-functional theory. Furthermore, the newly parametrized model is found to predict equilibrium geometries, binding energies, and vibrational frequencies for small aqueous clusters containing halogen anions, X(-)(H2O)n (n = 1-4), in good agreement with those calculated with density-functional theory and high-level ab initio quantum chemistry and with available experimental data. This demonstrates that the newly parametrized models might be a method of choice for investigating halide hydration in larger clusters.