TY - JOUR
T1 - The Impact of Coordination Environment on the Thermodynamic Stability of Uranium Oxides
AU - Shields, Ashley E.
AU - Miskowiec, Andrew J.
AU - Maheshwari, Ketan
AU - Kirkegaard, Marie C.
AU - Staros, Daniel J.
AU - Niedziela, Jennifer L.
AU - Kapsimalis, Roger J.
AU - Anderson, Brian B.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/7/5
Y1 - 2019/7/5
N2 - Amorphous uranium oxides are known to arise via industrial processes relevant to the nuclear fuel cycle yet evade rigorous structural characterization. A promising approach is to develop statistical relationships between uranium-oxygen coordination environments and thermodynamic stability from which general statements about the likelihood of observing particular U-O arrangements can be made. The number of known crystalline uranium oxides is insufficient to build statistical relationships. We have developed a database of theoretical compounds using genetic algorithms with the density functional theory as a foundation to analyze coordination geometries in the uranium-oxygen phase space. We draw fundamental insights into the nature of uranium-oxygen interactions by correlating total energy with the coordination environment. The most stable configuration of U cations with O anions is in an environment with coordination numbers 5-8 in a cubic configuration. Higher and lower coordination numbers are observed only in metastable phases. General trends are observable in the relationships between the coordination number, density, and uranium fraction in each structure. The new insight into uranium coordination enabled by these analyses is foundational for further studies into the characteristic properties of individual uranium oxide materials and for elucidation of potential oxidation pathways for uranium metal.
AB - Amorphous uranium oxides are known to arise via industrial processes relevant to the nuclear fuel cycle yet evade rigorous structural characterization. A promising approach is to develop statistical relationships between uranium-oxygen coordination environments and thermodynamic stability from which general statements about the likelihood of observing particular U-O arrangements can be made. The number of known crystalline uranium oxides is insufficient to build statistical relationships. We have developed a database of theoretical compounds using genetic algorithms with the density functional theory as a foundation to analyze coordination geometries in the uranium-oxygen phase space. We draw fundamental insights into the nature of uranium-oxygen interactions by correlating total energy with the coordination environment. The most stable configuration of U cations with O anions is in an environment with coordination numbers 5-8 in a cubic configuration. Higher and lower coordination numbers are observed only in metastable phases. General trends are observable in the relationships between the coordination number, density, and uranium fraction in each structure. The new insight into uranium coordination enabled by these analyses is foundational for further studies into the characteristic properties of individual uranium oxide materials and for elucidation of potential oxidation pathways for uranium metal.
UR - http://www.scopus.com/inward/record.url?scp=85068446846&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.9b03274
DO - 10.1021/acs.jpcc.9b03274
M3 - Article
AN - SCOPUS:85068446846
SN - 1932-7447
VL - 123
SP - 15985
EP - 15995
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
IS - 26
ER -