High-Resolution Solid-State Oxygen-17 NMR of Actinide-Bearing Compounds: An Insight into the 5f Chemistry

Martel, Laura and Magnani, Nicola and Vigier, Jean-Francois and Boshoven, Jacobus and Selfslag, Chris and Farnan, Ian and Griveau, Jean-Christophe and Somers, Joseph and Fanghänel, Thomas (2014) High-Resolution Solid-State Oxygen-17 NMR of Actinide-Bearing Compounds: An Insight into the 5f Chemistry. Inorganic Chemistry, 53 (13). pp. 6928-6933. ISSN 0020-1669, ESSN: 1520-510X DOI 10.1021/ic5007555

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Official URL: http://dx.doi.org/10.1021/ic5007555

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 (\textgreater55 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.

Item Type: Article
Uncontrolled Keywords: 2014AREP; IA68;
Subjects: 03 - Mineral Sciences
Divisions: 03 - Mineral Sciences
Journal or Publication Title: Inorganic Chemistry
Volume: 53
Page Range: pp. 6928-6933
Identification Number: 10.1021/ic5007555
Depositing User: Sarah Humbert
Date Deposited: 25 Aug 2014 14:41
Last Modified: 07 Sep 2014 01:47
URI: http://eprints.esc.cam.ac.uk/id/eprint/3106

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