Systematic Design-of-Experiments, factorial-design approaches for tuning simple empirical water models

Using systematic Design-of-Experiments, factorial-design approaches, we identify how five variables (site charge, sigma, epsilon, OH bond length and HOH bond angle) affect the diffusivity and radial distribution function accuracy within the framework of the Simple Point Charge water model. From this (by a full-functional DoX-effects model), we glean response equations for the effects of these systematic variations on both estimation of site-site radial distribution functions, in addition to self-diffusivities, allowing scope to estimate more precisely optimal parameters for use in tailored force-fields for particular purposes (e.g. improved fidelity towards particular desired structural or dynamical properties). To this end, the diffusivity error was reduced from an initial value of 35.2–0.64%, whilst the radial distribution function was more difficult to improve, with a reduction in error of 2.83%.