A massive interest has been generated lately by the improvement of solid-state magic-angle spinning (MAS) NMR methods for the study of a broad range of paramagnetic organic and inorganic materials. The open-shell cations at the origin of this paramagnetism can be metals, transition metals, or rare-earth elements. Actinide-bearing compounds and their 5f unpaired electrons remain elusive in this intensive research area due to their well-known high radiotoxicity. A dedicated effort enabling the handling of these highly radioactive materials now allows their analysis using high-resolution MAS NMR (>55 kHz). Here, the study of the local structure of a series of actinide dioxides, namely, ThO2, UO2, NpO2, PuO2, and AmO2, using solid-state 17O MAS NMR is reported. An important increase of the spectral resolution is found due to the removal of the dipolar broadening proving the efficiency of this technique for structural analysis. The NMR parameters in these systems with numerous and unpaired 5f electrons were interpreted using an empirical approach. Single-ion model calculations were performed for the first time to determine the z component of electron spin on each of the actinide atoms, which is proportional to the shifts. A similar variation thereof was observed only for the heavier actinides of this study.

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Safe management of high level nuclear waste is a worldwide significant issue for which vitrification has been selected by many countries. There exists a crucial need for improving our understanding of the ageing of the glass under irradiation. While external irradiation by ions provides a rapid simulation of damage induced by alpha decays, short lived actinide doping is more representative of the reality. Here, we report radiological NMR experiments to compare the damage in International Simplified Glass (ISG) when irradiated by these two methods. In the 0.1 mole percent 244Cm doped glass, accumulation of high alpha decay only shows small modifications of the local structure, in sharp contrast to heavy ion irradiation. These results reveal the ability of the alpha particle to partially repair the damage generated by the heavy recoil nuclei highlighting the radiation resistance of nuclear glass and the difficulty to accurately simulate its behaviour by single ion beam irradiations.

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