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 (ThO, PaO, UO, PaO(OH), UO(OH), UO, NpO, NpO(OH), and PuO(OH)) were calculated at the CCSD(T) level. The first step is the formation of a Lewis acid/base adduct with HO (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 HO addition was predicted to be exothermic, ca.