Structure, Spectroscopy, and Theoretical Analysis of Zero- and Three-Dimensional Lithium Plutonium Fluorides: Li4PuF8 and LiPuF5
| Autor: | Dayán Páez-Hernández, Thomas E. Albrecht-Schmitt, Alexander T. Chemey, Joseph M. Sperling, Cristian Celis-Barros |
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| Rok vydání: | 2019 |
| Předmět: |
Absorption spectroscopy
010405 organic chemistry Chemistry Atoms in molecules 010402 general chemistry 01 natural sciences Bond order 0104 chemical sciences Inorganic Chemistry Crystallography Covalent bond Intramolecular force Molecule Molecular orbital Physical and Theoretical Chemistry Spectroscopy |
| Zdroj: | Inorganic Chemistry. 58:14790-14799 |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
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