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Title: Bonding trends across the series of tricarbonato-actinyl anions [(AnO 2)(C 3) 3] 4- (An = U–Cm): the plutonium turn

Abstract

Actinyl-tricarbonato anions [(AnO 2)(CO 3) 3] 4- (An = U-Cm) in various environments were investigated using theoretical approaches of quantum-mechanics, molecular-mechanics and cluster-models. Cations and solvent molecules in the 2 nd coordination sphere affect the equatorial An←O eq bonds more than the axial An$$\equiv$$O ax bonds. Common actinide contraction is found for calculated and experimental axial bond lengths of 92U to 94Pu, though no longer for 94Pu to 96Cm. The tendency of U to Pu forming actinyl(vi) species dwindles away toward Cm, which already features the preferred An III/Ln III oxidation state of the later actinides and all lanthanides. The well known change from d-type to typical U-Pu-Cm type and then to f-type behavior is labeled as the plutonium turn, a phenomenon that is caused by f-orbital energy-decrease and f-orbital localization with increase of both nuclear charge and oxidation state, and a non-linear variation of effective f-electron population across the actinide series. Both orbital and configuration mixing and occupation of antibonding 5f type orbitals increase, weakening the AnO ax bonds and reducing the highest possible oxidation states of the later actinides.

Authors:
; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1372979
Report Number(s):
PNNL-SA-125514
Journal ID: ISSN 1477-9226; 47951; KP1704020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 46; Journal Issue: 8; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Liu, Jian-Biao, Chen, Guo P., Huang, Wei, Clark, David L., Schwarz, W. H. Eugen, and Li, Jun. Bonding trends across the series of tricarbonato-actinyl anions [(AnO2)(C3) 3] 4- (An = U–Cm): the plutonium turn. United States: N. p., 2017. Web. doi:10.1039/C6DT03953G.
Liu, Jian-Biao, Chen, Guo P., Huang, Wei, Clark, David L., Schwarz, W. H. Eugen, & Li, Jun. Bonding trends across the series of tricarbonato-actinyl anions [(AnO2)(C3) 3] 4- (An = U–Cm): the plutonium turn. United States. doi:10.1039/C6DT03953G.
Liu, Jian-Biao, Chen, Guo P., Huang, Wei, Clark, David L., Schwarz, W. H. Eugen, and Li, Jun. Sun . "Bonding trends across the series of tricarbonato-actinyl anions [(AnO2)(C3) 3] 4- (An = U–Cm): the plutonium turn". United States. doi:10.1039/C6DT03953G.
@article{osti_1372979,
title = {Bonding trends across the series of tricarbonato-actinyl anions [(AnO2)(C3) 3] 4- (An = U–Cm): the plutonium turn},
author = {Liu, Jian-Biao and Chen, Guo P. and Huang, Wei and Clark, David L. and Schwarz, W. H. Eugen and Li, Jun},
abstractNote = {Actinyl-tricarbonato anions [(AnO2)(CO3)3]4- (An = U-Cm) in various environments were investigated using theoretical approaches of quantum-mechanics, molecular-mechanics and cluster-models. Cations and solvent molecules in the 2nd coordination sphere affect the equatorial An←Oeq bonds more than the axial An$\equiv$Oax bonds. Common actinide contraction is found for calculated and experimental axial bond lengths of 92U to 94Pu, though no longer for 94Pu to 96Cm. The tendency of U to Pu forming actinyl(vi) species dwindles away toward Cm, which already features the preferred AnIII/LnIII oxidation state of the later actinides and all lanthanides. The well known change from d-type to typical U-Pu-Cm type and then to f-type behavior is labeled as the plutonium turn, a phenomenon that is caused by f-orbital energy-decrease and f-orbital localization with increase of both nuclear charge and oxidation state, and a non-linear variation of effective f-electron population across the actinide series. Both orbital and configuration mixing and occupation of antibonding 5f type orbitals increase, weakening the AnOax bonds and reducing the highest possible oxidation states of the later actinides.},
doi = {10.1039/C6DT03953G},
journal = {Dalton Transactions},
issn = {1477-9226},
number = 8,
volume = 46,
place = {United States},
year = {2017},
month = {1}
}

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