Molecular models of hydroxide, oxyhydroxide, and clay phases and the development of a general force field

The fate of chemical and radioactive wastes in the environment is related to the ability of natural phases to attenuate and immobilize contaminants through chemical sorption and precipitation processes. Our understanding of these complex processes at the atomic level is provided by a few experimental and analytical methods such as X-ray absorption and NMR spectroscopies. However, due to complexities in the structure and composition of clay and other hydrated minerals, and the inherent uncertainties of the experimental methods, it is important to apply theoretical molecular models for a fundamental atomic-level understanding, interpretation, and prediction of these phenomena. In this effort, we have developed a general force field, CLAYFF, suitable for the simulation of hydrated and multicomponent mineral systems and their interfaces with aqueous solutions. Interatomic potentials were derived from parametrizations incorporating structural and spectroscopic data for a variety of simple hydrated compounds. A flexible SPC-based water model is used to describe the water and hydroxyl behavior. Metal-oxygen interactions are described by a Lennard-Jones function and a Coulombic term with partial charges derived by Mulliken and ESP analysis of DFT results. Bulk structures, relaxed surface structures, and intercalation processes are evaluated and compared to experimental and spectroscopic findings for validation. Our approach differs from most others in that we treat most interatomic interactions as nonbonded. This allows us to effectively use the force field for a wide variety of phases and to properly account for energy and momentum transfer between the fluid phase and the solid, while keeping the number of parameters small enough to allow modeling of relatively large and highly disordered systems. Simulations of clay, hydroxide, and oxyhydroxide phases and their interfaces with aqueous solutions combine energy minimization and molecular dynamics methods to describe the structure and behavior of water, hydroxyl, surface species, and intercalates in these systems. The results obtained to date demonstrate that CLAYFF shows good promise to evolve into a widely adaptable and broadly effective force field for molecular simulations of fluid interfaces with clays and other clay-related phases, as well as other inorganic materials characterized by complex, disordered, and often ill-determined structure and composition.