Modeling Adsorption of the Uranyl Dication on the Hydroxylated α-Al2O3(0001) Surface in an Aqueous Medium. Density Functional Study

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Abstract
As a first step toward modeling the interaction of dissolved actinide contaminants with mineral surfaces, we studied low-coverage adsorption of aqueous uranyl, UO22+, on the hydroxylated α-Al2O3(0001) surface. We carried out density functional periodic slab model calculations and modeled solvation effects by explicit aqua ligands. We explored the formation of both inner- and outer-sphere complexes and estimated the corresponding adsorption energies. Effects of solvation were accounted for by explicit consideration of the first hydration shell of uranyl and by means of a posteriori corrections for long-range solvent effect. With energetics described at the GGA-PW91 level and under the assumption of a fully protonated ideal surface, we predict a weakly bound outer-sphere adsorption complex.