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Title: First principles investigation of the structural and bonding properties of hydrated actinide (IV) oxalates, An(C2O4)2·6H2O (An = U, Pu)

Abstract

The structural and bonding properties of actinide (IV) oxalates, U(C2O4)2·6H2O and Pu(C2O4)2·6H2O, are investigated using the generalized gradient approximation (GGA) to spin-polarized density functional theory (DFT) with van der Waals (vdW) corrections. The GGA optimized structures, ground state magnetic moments, site-projected density of states, and Bader charges are reported. We calculate the energy differences between ferromagnetic (FM) and antiferromagnetic (AFM) spin configurations on the Pu or U sites to determine the preferred magnetic structure of these materials. For both U(C2O4)2·6H2O and Pu(C2O4)2·6H2O, the relaxed FM-spin structures were found to be higher in energy than the corresponding relaxed AFM-spin structures. The density of states based on AFM-spin configuration do not reveal a significant energy gap near the Fermi level of either system; however, hybridization between the actinide (Pu or U) 5f and O (2p) states is evident. Bader charge analysis also reveals significant covalent contributions in the An-O bonds of the actinide-oxalate layer of both U(C2O4)2·6H2O and Pu(C2O4)2·6H2O systems.

Authors:
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  1. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1557147
Report Number(s):
PNNL-SA-133111
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Computational Materials Science
Additional Journal Information:
Journal Volume: 153
Country of Publication:
United States
Language:
English
Subject:
plutonium oxalate, uranium oxalate, Density Functional Theory, electronic structure

Citation Formats

Garrett, Kerry E., Ritzmann, Andrew M., Smith, Frances N., Kessler, Sean H., Devanathan, Ram, Henson, Neil J., and Abrecht, David G. First principles investigation of the structural and bonding properties of hydrated actinide (IV) oxalates, An(C2O4)2·6H2O (An = U, Pu). United States: N. p., 2018. Web. doi:10.1016/j.commatsci.2018.06.033.
Garrett, Kerry E., Ritzmann, Andrew M., Smith, Frances N., Kessler, Sean H., Devanathan, Ram, Henson, Neil J., & Abrecht, David G. First principles investigation of the structural and bonding properties of hydrated actinide (IV) oxalates, An(C2O4)2·6H2O (An = U, Pu). United States. doi:10.1016/j.commatsci.2018.06.033.
Garrett, Kerry E., Ritzmann, Andrew M., Smith, Frances N., Kessler, Sean H., Devanathan, Ram, Henson, Neil J., and Abrecht, David G. Mon . "First principles investigation of the structural and bonding properties of hydrated actinide (IV) oxalates, An(C2O4)2·6H2O (An = U, Pu)". United States. doi:10.1016/j.commatsci.2018.06.033.
@article{osti_1557147,
title = {First principles investigation of the structural and bonding properties of hydrated actinide (IV) oxalates, An(C2O4)2·6H2O (An = U, Pu)},
author = {Garrett, Kerry E. and Ritzmann, Andrew M. and Smith, Frances N. and Kessler, Sean H. and Devanathan, Ram and Henson, Neil J. and Abrecht, David G.},
abstractNote = {The structural and bonding properties of actinide (IV) oxalates, U(C2O4)2·6H2O and Pu(C2O4)2·6H2O, are investigated using the generalized gradient approximation (GGA) to spin-polarized density functional theory (DFT) with van der Waals (vdW) corrections. The GGA optimized structures, ground state magnetic moments, site-projected density of states, and Bader charges are reported. We calculate the energy differences between ferromagnetic (FM) and antiferromagnetic (AFM) spin configurations on the Pu or U sites to determine the preferred magnetic structure of these materials. For both U(C2O4)2·6H2O and Pu(C2O4)2·6H2O, the relaxed FM-spin structures were found to be higher in energy than the corresponding relaxed AFM-spin structures. The density of states based on AFM-spin configuration do not reveal a significant energy gap near the Fermi level of either system; however, hybridization between the actinide (Pu or U) 5f and O (2p) states is evident. Bader charge analysis also reveals significant covalent contributions in the An-O bonds of the actinide-oxalate layer of both U(C2O4)2·6H2O and Pu(C2O4)2·6H2O systems.},
doi = {10.1016/j.commatsci.2018.06.033},
journal = {Computational Materials Science},
number = ,
volume = 153,
place = {United States},
year = {2018},
month = {10}
}