Heptavalent Actinide Tetroxides NpO4– and PuO4–: Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO4

Gibson, John K.; de Jong, Wibe A.; Dau, Phuong D.; Gong, Yu

doi:10.1021/acs.jpca.7b09721

Heptavalent Actinide Tetroxides NpO₄^– and PuO₄^–: Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO₄

Journal Article · Tue Nov 14 00:00:00 EST 2017 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.7b09721· OSTI ID:1436653

^[1]; ^[1]; Dau, Phuong D. ^[1]; ^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO₃(NO₃)₂-, was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified. Reported here are the gas-phase syntheses and characterizations of NpO₄^- and PuO₄^-. Reactivity studies and density functional theory computations indicate the heptavalent metal oxidation state in both. This is the first instance of Pu(VII) in the absence of stabilizing effects due to condensed phase solvation or crystal fields. Here, the results indicate that addition of an electron to neutral PuO₄, which has a computed electron affinity of 2.56 eV, counterintuitively results in oxidation of Pu(V) to Pu(VII), concomitant with superoxide reduction.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1436653

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 47 Vol. 121; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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