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

Abstract

Abstract Actinyl chemistry is extended beyond Cm to BkO 2 + and CfO 2 + through transfer of an O atom from NO 2 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 AnO 2 + for An=Pa to Lr reveal an unexpected minimum for D[O‐(CmO + )]. For CmO 2 + , and AnO 2 + beyond EsO 2 + , the most stable structure has side‐on bonded η 2 ‐(O 2 ), 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 EsO 2 + is linear [O=Es V =O] + , einsteinyl, and that FmO 2 + and MdO 2 + , like CmO 2 + , also have actinyl(V) structures as local energy minima. The results expand actinide oxidation state chemistry, the realmmore » of the distinctive actinyl moiety, and the non‐periodic character towards the end of the periodic table.« less

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [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
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Nuclear Physics (NP)
OSTI Identifier:
1418310
Alternate Identifier(s):
OSTI ID: 1408259
Grant/Contract Number:  
AC02-05CH11231; FG02-12ER16329
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 23; Journal Issue: 68; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; actinides; density functional calculations; gas-phase reactions; redox chemistry; transuranium elements

Citation Formats

Dau, Phuong D., Vasiliu, Monica, Peterson, Kirk A., Dixon, David A., and Gibson, John K.. Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium. United States: N. p., 2017. Web. doi:10.1002/chem.201704193.
Dau, Phuong D., Vasiliu, Monica, Peterson, Kirk A., Dixon, David A., & Gibson, John K.. Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium. United States. https://doi.org/10.1002/chem.201704193
Dau, Phuong D., Vasiliu, Monica, Peterson, Kirk A., Dixon, David A., and Gibson, John K.. Thu . "Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium". United States. https://doi.org/10.1002/chem.201704193. https://www.osti.gov/servlets/purl/1418310.
@article{osti_1418310,
title = {Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium},
author = {Dau, Phuong D. and Vasiliu, Monica and Peterson, Kirk A. and Dixon, David A. and Gibson, John K.},
abstractNote = {Abstract Actinyl chemistry is extended beyond Cm to BkO 2 + and CfO 2 + through transfer of an O atom from NO 2 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 AnO 2 + for An=Pa to Lr reveal an unexpected minimum for D[O‐(CmO + )]. For CmO 2 + , and AnO 2 + beyond EsO 2 + , the most stable structure has side‐on bonded η 2 ‐(O 2 ), 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 EsO 2 + is linear [O=Es V =O] + , einsteinyl, and that FmO 2 + and MdO 2 + , like CmO 2 + , also have actinyl(V) structures as local energy minima. 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.},
doi = {10.1002/chem.201704193},
journal = {Chemistry - A European Journal},
number = 68,
volume = 23,
place = {United States},
year = {Thu Oct 12 00:00:00 EDT 2017},
month = {Thu Oct 12 00:00:00 EDT 2017}
}

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