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

Journal Article · · Chemistry - A European Journal
 [1];  [2];  [3];  [2];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Univ. of Alabama, Tuscaloosa, AL (United States). Dept. of Chemistry
  3. Washington State Univ., Pullman, WA (United States). Dept. of Chemistry
+ Show Author Affiliations
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 AnII superoxides for An=Fm, Md, and No. It is predicted that the most stable structure of EsO2+ is linear [O=EsV =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.
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
Alternate ID(s):
OSTI ID: 1408259
OSTI ID: 22725453
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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Figures / Tables (7)

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Related Subjects

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