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Uranyl-peroxide Nanocapsules in Aqueous Solution: Force Field Development and First Applications

Miró, P.; Vlaisavljevich, B.; Dzubak, A. L.; Hu, S.; Burns, P. C.; Cramer, C. J.; Spezia, R.; Gagliardi, L.
J. Phys. Chem. C 2014, 118, 24730 (doi:10.1021/jp504147s).

The self-assembly of uranyl-peroxide nanocapsules in aqueous solution is unique in uranium chemistry and has potential applications in the fabrication and reprocessing of actinide-based materials. We present the first study of these species in aqueous solution by means of classical molecular dynamics simulations. To this end, we parameterized a uranyl-peroxide force field from interaction energies computed with second order Møller-Plesset perturbation theory and fit to a Born-Huggins-Mayer potential. Bonded parameters were fit from density functional theory calculations. The solvent and counterion structure surrounding four different systems ([(UVIO2)]2+, [(UVIO2)22-O2)]2+, [(UVIO2)52-O2)5] and [(UVIO2)202-O2)30]20-) was studied in aqueous solution. The largest studied system is predicted to encapsulate an ice-like water cluster.