Structure, Spectroscopy, and Theoretical Analysis of Zero- A nd Three-Dimensional Lithium Plutonium Fluorides: Li4PuF8 and LiPuF5

Alexander T. Chemey, Cristian Celis-Barros, Joseph M. Sperling, Dayán Paéz-Hernández, Thomas E. Albrecht-Schmitt

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

6 Citas (Scopus)

Resumen

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.

Idioma originalInglés
Páginas (desde-hasta)14790-14799
Número de páginas10
PublicaciónInorganic Chemistry
Volumen58
N.º21
DOI
EstadoEn prensa - 1 ene 2019

Áreas temáticas de ASJC Scopus

  • Química física y teórica
  • Química inorgánica

Huella

Profundice en los temas de investigación de 'Structure, Spectroscopy, and Theoretical Analysis of Zero- A nd Three-Dimensional Lithium Plutonium Fluorides: Li<sub>4</sub>PuF<sub>8</sub> and LiPuF<sub>5</sub>'. En conjunto forman una huella única.

Citar esto