Cluster-models for uranyl(VI) adsorption on α-alumina

Aqueous complexation, adsorption, and redox chemistry of actinide species at mineral surfaces have a significant impact on their transport and reactive behavior in chemically and physically heterogeneous environments. The adsorption configurations and energies of microsolvated uranyl dication species, UO ₂(H₂O)_n²⁺, were determined on fully hydroxylated and proton-deficient α-alumina(0001)-like finite cluster models. The significant size of the models provides faithful representations of features that have emerged from periodic calculations, but most importantly, they afford us a systematic study of the adsorption mechanism, the effect of secondary solvation shells and an explicit treatment of the total charge. Based on this cluster representation, the energetics computed from the difference between the optimized structures and the appropriate reference states point to a preference for an inner-sphere type complex.