Hydrolysis Reactions of the High Oxidation State Dimers Th2O4, Pa2O5, U2O6, and Np2O6. A Computational Study.

The energetics of the hydrolysis reactions for high oxidation states of the dimeric actinide species Th2IVO4, Pa2VO5, and U2VIO6 were calculated at the CCSD(T) level and those for triplet Np2VIO6 at the B3LYP level. Hydrolysis is initiated by the formation of a Lewis acid/base adduct with H2O (physisorbed product), followed by a proton transfer to form a dihydroxide molecule (chemisorbed product); this process was repeated until the initial actinide oxide is fully hydrolyzed. For Th2O4, hydrolysis (chemisorption) by the initial and subsequent H2O molecules prefers proton transfer to terminal oxo groups before the bridge oxo groups. The overall Th2O4 hydration pathway is exothermic with chemisorbed products preferred over the physisorption products, and the fully hydrolyzed Th2(OH)8 can form exothermically. Hydrolysis of Pa2O5 forms isomers of similar energies with no initial preference for bridge or terminal hydroxy groups. The most exothermic hydrolysis product for Pa is Pa2O(OH)8 and the most stable species is Pa2O(OH)8(H2O). Hydrolysis of U2O6 and Np2O6 with strong [O═An═O]2+ actinyl groups occurs first at the bridging oxygens rather than at the terminal oxo groups. The U2O6 and Np2O6 pathways predict hydrated products to be more favored than hydrolyzed products, as more H2O molecules are added. The stability of the U and Np clusters is predicted to decrease with increasing number of hydroxyl groups. The most stable species on the hydration reaction coordinate for U and Np is An2O3(OH)6(H2O).

Hydrolysis of Small Oxo/Hydroxo Molecules Containing High Oxidation State Actinides (Th, Pa, U, Np, Pu): A Computational Study.

The energetics of hydrolysis reactions for high oxidation states of oxo/hydroxo monomeric actinide species (ThIVO2, PaIVO2, UIVO2, PaVO2(OH), UVO2(OH), UVIO3, NpVIO3, NpVIIO3(OH), and PuVIIO3(OH)) were calculated at the CCSD(T) level. The first step is the formation of a Lewis acid/base adduct with H2O (hydration), followed by a proton transfer to form a dihydroxide molecule (hydrolysis); this process is repeated until all oxo groups are hydrolyzed. The physisorption (hydration) for each H2O addition was predicted to be exothermic, ca. -20 kcal/mol. The hydrolysis products are preferred energetically over the hydration products for the +IV and +V oxidation states. The compounds with AnVI are a turning point in terms of favoring hydration over hydrolysis. For AnVIIO3(OH), hydration products are preferred, and only two waters can bind; the complete hydrolysis process is now endothermic, and the oxidation state for the An in An(OH)7 is +VI with two OH groups each having one-half an electron. The natural bond order charges and the reaction energies provide insights into the nature of the hydrolysis/hydration processes. The actinide charges and bond ionicity generally decrease across the period. The ionic character decreases as the oxidation state and coordination number increase so that covalency increases moving to the right in the actinide period.