Accurate SCC-DFTB Parametrization for Bulk Water

The SCC-DFTB repulsion parameters based on the material science set (matsci) were redesigned to describe the structure and dynamic properties of bulk liquid water. The iterative Boltzman inversion (IBI) approach was applied by simultaneously correcting the O–H and O–O SCC-DFTB repulsion energy contribution to develop the new water–matsci and water–matsci–UFF set of parameters. The water–matsci parameters provide O–O and O–H radial distribution functions in excellent agreement with available state-of-the-art experimental data. The parametrization is applied to compute binding energies of a set of water clusters with 2–10 molecules and compared to other DFTB parameters and reference data. The self-diffusion coefficients of ambient and supercooled (254 K) water have been estimated and compared to other SCC-DFTB calculated values and experiment. The performance of the new parameters for describing the density of ambient water and reactions involving water dissociation into H₃O⁺ and OH^–, the self-diffusion coefficient, and neutralization energy were investigated. Finally, we show that the new parametrization can be reliably applied to adsorption of water on the mineral pyrite by combining the new water–matsci parameters with the available matsci set of parameters for pyrite. This opens opportunities for investigating materials and phenomena of increasing complexity involving water.