Structure and hydrolysis of the U(IV), U(V), and U(VI) aqua ions from ab initio molecular simulations.

Ab initio molecular dynamics simulations at 300 K, based on density functional theory, are performed to study the hydration shell geometries, solvent dipole, and first hydrolysis reaction of the uranium(IV) (U(4+)) and uranyl(V) (UO(2)(+)) ions in aqueous solution. The solvent dipole and first hydrolysis reaction of aqueous uranyl(VI) (UO(2)(2+)) are also probed. The first shell of U(4+) is coordinated by 8-9 water ligands, with an average U-O distance of 2.42 Å. The average first shell coordination number and distance are in agreement with experimental estimates of 8-11 and 2.40-2.44 Å, respectively. The simulated EXAFS of U(4+) matches well with recent experimental data. The first shell of UO(2)(+) is coordinated by five water ligands in the equatorial plane, with the average U═O(ax) and U-O distances being 1.85 Å and 2.54 Å, respectively. Overall, the hydration shell structure of UO(2)(+) closely matches that of UO(2)(2+), except for small expansions in the average U═O(ax) and U-O distances. Each ion strongly polarizes their respective first-shell water ligands. The computed acidity constants (pK(a)) of U(4+) and UO(2)(2+) are 0.93 and 4.95, in good agreement with the experimental values of 0.54 and 5.24, respectively. The predicted pK(a) value of UO(2)(+) is 8.5.