The potential energy surfaces for the reactions of H2O with ThO2, PaO2+, UO22+, and UO2+ have been calculated at the coupled cluster CCSD(T) level extrapolated to the complete basis set limit with additional correctiOns including, scalar relativistic and spin orbit The reactions proceed by the formation of an initial Lewis acid base, adduct (H2O)AnO(2)(0/+/2+) followed by a proton transfer to generate the dihydroxide AnO(OH)(2)(0/+/2+). The results are in excellent agreement with mass, spectrometry experiments and prior calculations of hydrolysis reactions of the group 4: transition metal dioxides MO2. The differences in the energies Of the stationary points on the potential energy surface are explained in terms-of the charges on, the-system and the populations on the metal center. The use of an improved starting,point for the coupled cluster CCSD(T) calculations based On density functional theory with the PW91 exchange-correlaticin functional: or Brueckner,orbitals-is described. The importance of including second-order spin orbit corrections for closed-shell molecules is also described. These improvements in the calculations are correlated with the 5f populations on the actinide.