Title: Pentavalent Curium, Berkelium, and Californium in Nitrate Complexes: Extending Actinide Chemistry and Oxidation States
Authors: KOVACS ATTILADAU PHUONG D.MARCALO JOAQUIMGIBSON JOHN K.
Citation: INORGANIC CHEMISTRY vol. 57 no. 15 p. 9453-9467
Publisher: AMER CHEMICAL SOC
Publication Year: 2018
JRC N°: JRC112062
ISSN: 0020-1669 (online)
URI: http://publications.jrc.ec.europa.eu/repository/handle/JRC112062
DOI: 10.1021/acs.inorgchem.8b01450
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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