Lawrence Berkeley National Laboratory

Pentavalent actinyl nitrate complexes An^VO₂(NO₃)₂^- were produced by elimination of two NO₂ from An^III(NO₃)₄^- for An = Pu, Am, Cm, Bk, and Cf. Density functional theory (B3LYP) and relativistic multireference (CASPT2) calculations confirmed the AnO₂(NO₃)₂^- as An^VO₂⁺ actinyl moieties coordinated by nitrates. Computations of alternative An^IIIO₂(NO₃)₂^- and An^IVO₂(NO₃)₂^- revealed significantly higher energies. Previous computations for bare AnO₂⁺ indicated An^VO₂⁺ for An = Pu, Am, Cf, and Bk, but Cm^IIIO₂⁺: electron donation from nitrate ligands has here stabilized the first Cm^V complex, Cm^VO₂(NO₃)₂^-. Structural parameters and bonding analyses indicate increasing An-NO₃ bond covalency from Pu to Cf, in accordance with principles for actinide separations. Atomic ionization energies effectively predict relative stabilities of oxidation states; more reliable energies are needed for the actinides.