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|Title:||Pentavalent Curium, Berkelium, and Californium in Nitrate Complexes: Extending Actinide Chemistry and Oxidation States|
|Authors:||KOVACS ATTILA; DAU PHUONG D.; MARCALO JOAQUIM; GIBSON JOHN K.|
|Citation:||INORGANIC CHEMISTRY vol. 57 no. 15 p. 9453-9467|
|Publisher:||AMER CHEMICAL SOC|
|Type:||Articles in periodicals and books|
|Abstract:||Pentavalent actinyl nitrate complexes AnVO2(NO3)2- were produced by elimination of two NO2 from AnIII(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 AnVO2+ actinyl moieties coordinated by nitrates. Computations of alternative AnIIIO2(NO3)2- and AnIVO2(NO3)2- revealed significantly higher energies. Previous computations for bare AnO2+ indicated AnVO2+ for An = Pu, Am, Cf and Bk, but CmIIIO2+: electron donation from nitrate ligands has here stabilized the first CmV complex, CmVO2(NO3)2-. Structural parameters and bonding analyses indicate increasing An-NO3 bond covalency from Pu to Cf, in accord with principles for actinide separations. Atomic ionization energies effectively predict relative stabilities of oxidation states; more reliable energies are needed for the actinides.|
|JRC Directorate:||Nuclear Safety and Security|
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