Atomistic modeling of mineral–water interfaces offers a way of confirming (or refuting) experimental information about structure and reactivity. Molecular-level understanding, such as orbital-based descriptions of bonding, can be developed from charge density and electronic structure analysis. First-principles calculations can be used to identify weaknesses in empirical models. This provides direction on how to propose more robust representations of systems of increasing size that accurately represent the underlying physical factors governing reactivity. In this study, inner-sphere complex geometries of arsenate on hydrated alumina surfaces are modeled at the density functional theory (DFT)–continuum solvent level. According to experimental studies, arsenate binds to alumina surfaces in a bidentate binuclear (BB) fashion. While the DFT calculations support the preference of the BB configuration, the optimized geometries show distortion from the ideal tetrahedral geometry of the arsenic atom. This finding suggests that steric factors, and not just coordination arguments, influences reactivity. The Osurf
angle for the more favorable arsenate configurations is closest to the ideal tetrahedral angle of 109.5°. Comparing the results of arsenate adsorption using a small cluster model with a periodic slab model, we report that the two model geometries yield results that differ qualitatively and quantitatively. This relates the steric factors and rigidity of the surface models.
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