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Title: A Computational Assessment of Actinide Dioxide Cations AnO22+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O=An=O]2+

Abstract

In this work, the isolated gas-phase actinide dioxide dications, AnO22+, were evaluated by DFT and coupled cluster CCSD(T) calculations for 12 actinides, An = U–Lr. CASSCF calculations were used to define the orbitals for the CCSD(T) calculations. The characteristic linear [O$=$An$=$O]2+ hexavalent actinyl(VI) was found to be the lowest energy structure for An = U, Np, and Pu, which also form stable actinyl(VI) species in solution and possibly for Am when spin–orbit effects are included. For Am, there is a divalent [AnII(O2)]2+ structure where the dioxygen is an end-on physisorbed η1-3O2 2 kcal/mol above the actinyl when spin–orbit effects are included which lower the energy of the actinyl structure. For An = Cm, Bk, and Lr, the lowest energy structure is trivalent [AnIII(O2)]2+ where the dioxygen is a side-on superoxide, η2-O2. For Cm, the actinyl is close in energy to the ground state when spin–orbit effects are included. For An = Cf, Es, Fm, Md, and No, the lowest energy structure is divalent [AnII(O2)]2+ where the dioxygen is an end-on physisorbed η1-3O2. The relative energies suggest that curyl(VI) and berkelyl(VI), like well-known americyl(VI), might be stabilized by coordinating ligands in condensed phases. The results further indicate that for californyl andmore » beyond, the actinyl(VI) moieties will probably be elusive even using strong donor ligands. The prevalence of low oxidation states (OSs) An(II) and An(III) for transplutonium actinides reflects stabilization of the 5f orbitals and validates established trends, including the remarkably high stability of divalent No. Finally, bond distances and other parameters suggest maximum bond covalency around plutonyl(VI), with a particularly substantial decrease in bond strength between americyl(VI) and curyl(VI).« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of Alabama, Tuscaloosa, AL (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Washington State Univ., Pullman, WA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of Alabama, Tuscaloosa, AL (United States); Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1642682
Alternate Identifier(s):
OSTI ID: 1657536
Grant/Contract Number:  
AC02-05CH11231; SC0018921; SC00085019; SC0008501
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 59; Journal Issue: 7; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; group theory; chemical structure; oxygen; energy; quantum mechanics

Citation Formats

Vasiliu, Monica, Jian, Tian, Gibson, John K., Peterson, Kirk A., and Dixon, David A. A Computational Assessment of Actinide Dioxide Cations AnO22+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O=An=O]2+. United States: N. p., 2020. Web. doi:10.1021/acs.inorgchem.9b03690.
Vasiliu, Monica, Jian, Tian, Gibson, John K., Peterson, Kirk A., & Dixon, David A. A Computational Assessment of Actinide Dioxide Cations AnO22+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O=An=O]2+. United States. https://doi.org/10.1021/acs.inorgchem.9b03690
Vasiliu, Monica, Jian, Tian, Gibson, John K., Peterson, Kirk A., and Dixon, David A. Thu . "A Computational Assessment of Actinide Dioxide Cations AnO22+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O=An=O]2+". United States. https://doi.org/10.1021/acs.inorgchem.9b03690. https://www.osti.gov/servlets/purl/1642682.
@article{osti_1642682,
title = {A Computational Assessment of Actinide Dioxide Cations AnO22+ for An = U to Lr: The Limited Stability Range of the Hexavalent Actinyl Moiety, [O=An=O]2+},
author = {Vasiliu, Monica and Jian, Tian and Gibson, John K. and Peterson, Kirk A. and Dixon, David A.},
abstractNote = {In this work, the isolated gas-phase actinide dioxide dications, AnO22+, were evaluated by DFT and coupled cluster CCSD(T) calculations for 12 actinides, An = U–Lr. CASSCF calculations were used to define the orbitals for the CCSD(T) calculations. The characteristic linear [O$=$An$=$O]2+ hexavalent actinyl(VI) was found to be the lowest energy structure for An = U, Np, and Pu, which also form stable actinyl(VI) species in solution and possibly for Am when spin–orbit effects are included. For Am, there is a divalent [AnII(O2)]2+ structure where the dioxygen is an end-on physisorbed η1-3O2 2 kcal/mol above the actinyl when spin–orbit effects are included which lower the energy of the actinyl structure. For An = Cm, Bk, and Lr, the lowest energy structure is trivalent [AnIII(O2–)]2+ where the dioxygen is a side-on superoxide, η2-O2–. For Cm, the actinyl is close in energy to the ground state when spin–orbit effects are included. For An = Cf, Es, Fm, Md, and No, the lowest energy structure is divalent [AnII(O2)]2+ where the dioxygen is an end-on physisorbed η1-3O2. The relative energies suggest that curyl(VI) and berkelyl(VI), like well-known americyl(VI), might be stabilized by coordinating ligands in condensed phases. The results further indicate that for californyl and beyond, the actinyl(VI) moieties will probably be elusive even using strong donor ligands. The prevalence of low oxidation states (OSs) An(II) and An(III) for transplutonium actinides reflects stabilization of the 5f orbitals and validates established trends, including the remarkably high stability of divalent No. Finally, bond distances and other parameters suggest maximum bond covalency around plutonyl(VI), with a particularly substantial decrease in bond strength between americyl(VI) and curyl(VI).},
doi = {10.1021/acs.inorgchem.9b03690},
journal = {Inorganic Chemistry},
number = 7,
volume = 59,
place = {United States},
year = {2020},
month = {3}
}

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