Theoretical study of the microhydration of mononuclear and dinuclear uranium(VI) species derived from solvolysis of uranyl nitrate in water.

The structures and energetics of mononuclear and dinuclear uranium species formed upon speciation of uranyl(VI) nitrate, UO(2)(NO(3))(2), in water are investigated by quantum chemistry using density functional theory and the wavefunction-based methods (MP2, CCSD, CCSD(T)). We provide a discussion of the basic coordination patterns of the various mono- and dinuclear uranyl compounds (UO(2))(m)(X,Y)(2m-1)(H2O)(n) (m = 1, 2; n = 0-4) found in a recent mass spectrometric study (Tsierkezos et al., Inorg Chem 2009, 48, 6287). The energetics of the complexation of the uranyl dication to the counterions OH(-) and NO(3) (-) as well as the degradation of the dinuclear species were studied by reference to a test set of 16 representative molecules with the MP2 method and the B3LYP, M06, M06-HF, and M06-2X DFT functionals. All DFT functionals provide structures and energetics close to MP2 results, with M06 family being slightly superior to the standard B3LYP functional.