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.

Some example applications are presented, in which the peculiar Raman fingerprint of PuO₂ can be used for the detection of crystalline Pu⁴⁺ with cubic symmetry in an oxide environment in various host materials, like mixed oxide fuels, inert matrices and corium sub-systems. The PuO₂ Raman fingerprint was previously observed to consist of one main T_2g vibrational mode at 478 cm⁻¹ and two crystal electric field transition lines at 2130 cm⁻¹ and 2610 cm⁻¹. This particular use of Raman spectroscopy is promising for applications in nuclear waste management, safety and safeguard.