Density Functional Theory and Thermodynamics Modeling of Inner-Sphere Oxyanion Adsorption on the Hydroxylated...

The inner-sphere adsorption of AsO₄^3-, PO₄^3-, and SO₄^2- on the hydroxylated α-Al₂O₃(001) surface was modeled with the goal of adapting a density functional theory (DFT) and thermodynamics framework for calculating the adsorption energetics. While DFT is a reliable method for predicting various properties of solids, including crystalline materials comprised of hundreds (or even thousands) of atoms, adding aqueous energetics in heterogeneous systems poses steep challenges for modeling. This is in part due to the fact that environmentally relevant variations in the chemical surroundings cannot be captured atomistically without increasing the system size beyond tractable limits. The DFT + thermodynamics approach to this conundrum is to combine the DFT total energies with tabulated solution-phase data and Nernst-based corrective terms to incorporate experimentally tunable parameters such as concentration. Central to this approach is the design of thermodynamic cycles that partition the overall reaction (here, inner-sphere adsorption proceeding via ligand exchange) into elementary steps that can either be fully calculated or for which tabulated data are available. The ultimate goal is to develop a modeling framework that takes into account subtleties of the substrate (such as adsorption-induced surface relaxation) and energies associated with the aqueous environment such that adsorption at mineral-water interfaces can be reliably predicted, allowing for comparisons in the denticity and protonation state of the adsorbing species. Based on the relative amount of experimental information available for AsO₄^3-, PO₄^3-, and SO₄^2- adsorbates and the well-characterized hydroxylated α-Al₂O₃(001) surface, these systems are chosen to form a basis for assessing the model predictions. We discuss how the DFT + thermodynamics results are in line with the experimental information about the oxyanion sorption behavior. Additionally, a vibrational analysis was conducted for the charge-neutral oxyanion complexes and is compared to the available experimental findings to discern the inner-sphere adsorption phonon modes. The DFT + thermodynamics framework used here is readily extendable to other chemical processes at solid-liquid interfaces, and we discuss future directions for modeling surface processes at mineral-water and environmental interfaces.