High-Resolution Solid-State Oxygen-17 NMR of Actinide-Bearing
Compounds: An Insight into the 5f Chemistry
- Publication date
- Publisher
Abstract
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, ThO<sub>2</sub>, UO<sub>2</sub>, NpO<sub>2</sub>, PuO<sub>2</sub>, and AmO<sub>2</sub>, using solid-state <sup>17</sup>O 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 <i>z</i> 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