TY - JOUR
T1 - Structure, Spectroscopy, and Theoretical Analysis of Zero- A nd Three-Dimensional Lithium Plutonium Fluorides
T2 - Li4PuF8 and LiPuF5
AU - Chemey, Alexander T.
AU - Celis-Barros, Cristian
AU - Sperling, Joseph M.
AU - Paéz-Hernández, Dayán
AU - Albrecht-Schmitt, Thomas E.
N1 - Funding Information:
This research was supported by the Center for Actinide Science and Technology, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, under Award DE-SC0016568. Additional support was provided by Fondecyt Grant 1180017.
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/1/1
Y1 - 2019/1/1
N2 - The reaction of 242PuO2 with HF and LiF under hydrothermal conditions results in the formation of Li4PuF8 and LiPuF5. These compounds were structurally characterized using single-crystal X-ray diffraction, and UV-vis-near-IR absorption spectroscopy was employed to confirm the oxidation state of the plutonium in the compounds as 4+. The structure of Li4PuF8 consists of [PuF8]4- anions that adopt a bicapped trigonal-prismatic geometry with approximate C2v symmetry. These molecules are bridged by Li+ cations. In contrast, LiPuF5 forms a dense three-dimensional network constructed from [PuF9]5- units that are bridged by F- anions. The Pu4+ cations are found within tricapped trigonal prisms. Extensive theoretical analysis of the electronic and bonding interactions is included with a comparison between the results derived from complete-active-space self-consistent-field at different levels of theory, quantum theory of atoms in molecules, interacting quantum atom, natural localized molecular orbital, and Wiberg bond order analyses. Covalent interactions in these compounds are examined, and intramolecular trends in covalent and electrostatic interactions are discussed.
AB - The reaction of 242PuO2 with HF and LiF under hydrothermal conditions results in the formation of Li4PuF8 and LiPuF5. These compounds were structurally characterized using single-crystal X-ray diffraction, and UV-vis-near-IR absorption spectroscopy was employed to confirm the oxidation state of the plutonium in the compounds as 4+. The structure of Li4PuF8 consists of [PuF8]4- anions that adopt a bicapped trigonal-prismatic geometry with approximate C2v symmetry. These molecules are bridged by Li+ cations. In contrast, LiPuF5 forms a dense three-dimensional network constructed from [PuF9]5- units that are bridged by F- anions. The Pu4+ cations are found within tricapped trigonal prisms. Extensive theoretical analysis of the electronic and bonding interactions is included with a comparison between the results derived from complete-active-space self-consistent-field at different levels of theory, quantum theory of atoms in molecules, interacting quantum atom, natural localized molecular orbital, and Wiberg bond order analyses. Covalent interactions in these compounds are examined, and intramolecular trends in covalent and electrostatic interactions are discussed.
UR - http://www.scopus.com/inward/record.url?scp=85074421558&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.9b02466
DO - 10.1021/acs.inorgchem.9b02466
M3 - Article
C2 - 31647651
AN - SCOPUS:85074421558
SN - 0020-1669
VL - 58
SP - 14790
EP - 14799
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 21
ER -