MOLECULAR STATICS CALCULATIONS FOR IRON OXIDE AND OXYHYDROXIDE MINERALS: TOWARD A FLEXIBLE MODEL OF THE REACTIVE MINERAL-WATER INTERFACE

Abstract

Molecular statics calculations are used to model the major FeOOH polymorphs and hematite. The potentials were taken from a previous investigation of Fe(III) in aqueous solutions which involved the extrapolation of the gas-phase Fe(III)-OH2 potential energy surface to the solvated hexaaqua complex. Using this model for the solid phases, lattice parameters for goethite, akaganeite, lepidocrocite, and hematite are generally within 4% of experiment. Internal energies (at 0 K) were computed for each structure; lepidocrocite is energetically the most stable polymorph, followed by akaganeite, with goethite being the least stable. While the model exhibits some variances with experiment, it performs remarkably well, despite the challenging constraint of being consistent with a dissociating molecular dynamics model for water in its gas, aqueous, and solid phases. Because of this consistency, the model allows qualitative theoretical treatment of previously unapproachable problems in mineral-water interface geochemistry. We apply the model to identify surface species on the solvated (110) surface of goethite.