Insight into the Crystalline Structure of ThF<sub>4</sub> with the Combined Use of Neutron Diffraction, <sup>19</sup>F Magic-Angle Spinning-NMR, and Density Functional Theory Calculations

Journal article (2018)

Authors

L. Martel European Commission Joint Research Centre, Institute for Transuranium Elements Karlsruhe
E. Capelli RST/Reactor Physics and Nuclear Materials - AS
Monique Body Le Mans Université, Le Mans
Marco Klipfel Kerntechnische Entsorgung Karlsruhe, Eggenstein-Leopoldshafen
O. Beneš European Commission Joint Research Centre, Institute for Transuranium Elements Karlsruhe
Louis Maksoud Université d'Orléans
Philippe E. Raison European Commission Joint Research Centre, Institute for Transuranium Elements Karlsruhe
Emmanuelle Suard Institut Laue-Langevin
Lucas Visscher Vrije Universiteit Amsterdam
More Authors More Authors External organisation
Research Group
RST/Reactor Physics and Nuclear Materials (AS) (TU Delft)
More Info
expand_more

Published Date

2018

Language

English

Reuse Rights

Other than for strictly personal use, it is not permitted to download, forward or distribute the text or part of it, without the consent of the author(s) and/or copyright holder(s), unless the work is under an open content license such as Creative Commons.

Faculty

Applied Sciences

Department

RST/Radiation, Science and Technology

Research Group

RST/Reactor Physics and Nuclear Materials

Abstract

Because of its sensitivity to the atomic scale environment, solid-state NMR offers new perspectives in terms of structural characterization, especially when applied jointly with first-principles calculations. Particularly, challenging is the study of actinide-based materials because of the electronic complexity of the actinide cations and to the hazards due to their radioactivity. Consequently, very few studies have been published in this subfield. In the present paper, we report a joint experimental-theoretical analysis of thorium tetrafluoride, ThF4, containing a closed-shell actinide (5f0) cation. Its crystalline structure has been revisited in the present work using powder neutron diffraction experiments. The 19F NMR parameters of the seven F crystallographic sites have been modeled using an empirical superposition model, periodic first-principles calculations, and a cluster-based all-electron approach. On the basis of the atomic position optimized structure, a complete and unambiguous assignment of the 19F NMR resonances to the F sites has been obtained.