Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium

Dau, Phuong D.; Vasiliu, Monica; Peterson, Kirk A.; Dixon, David A.; Gibson, John K.

doi:10.1002/chem.201704193

Title: Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium

Journal Article · Thu Oct 12 00:00:00 UTC 2017 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.201704193 · OSTI ID:1418310

Dau, Phuong D. ^[1]; Vasiliu, Monica ^[2];

^[3];

^[2];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry
Washington State Univ., Pullman, WA (United States). Dept. of Chemistry

Actinyl chemistry is extended beyond Cm to BkO₂⁺ and CfO₂⁺ through transfer of an O atom from NO₂ to BkO⁺ or CfO⁺ , establishing a surprisingly high lower limit of 73 kcal mol^-1 for the dissociation energies, D[O-(BkO⁺)] and D[O-(CfO⁺)]. CCSD(T) computations are in accord with the observed reactions, and characterize the newly observed dioxide ions as linear pentavalent actinyls; these being the first Bk and Cf species with oxidation states above IV. Computations of actinide dioxide cations AnO₂⁺ for An=Pa to Lr reveal an unexpected minimum for D[O-(CmO⁺)]. For CmO₂⁺, and AnO₂⁺ beyond EsO₂⁺, the most stable structure has side-on bonded η² -(O₂), as An ^III peroxides for An=Cm and Lr, and as An^II superoxides for An=Fm, Md, and No. It is predicted that the most stable structure of EsO₂⁺ is linear [O=Es^V =O]⁺, einsteinyl, and that FmO₂⁺ and MdO₂⁺, like CmO₂⁺ , also have actinyl(V) structures as local energy minima. Finally, the results expand actinide oxidation state chemistry, the realm of the distinctive actinyl moiety, and the non-periodic character towards the end of the periodic table.

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

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Nuclear Physics (NP) (SC-26)

Grant/Contract Number:: AC02-05CH11231; SC0008501

OSTI ID:: 1418310

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 68 Vol. 23; ISSN 0947-6539

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
actinides
density functional calculations
gas-phase reactions
redox chemistry
transuranium elements

Title: Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium

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