Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series

Deblonde, Gauthier J. -P.; Kelley, Morgan P.; Su, Jing; Batista, Enrique R.; Yang, Ping; Booth, Corwin H.; Abergel, Rebecca J.

doi:10.1002/anie.201709183

Title: Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series

Journal Article · 22 February 2018 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.201709183 · OSTI ID:1477677

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Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Nuclear Engineering

The chemistry of trivalent transplutonium ions (Am³⁺, Cm³⁺, Bk³⁺, Cf³⁺, Es³⁺…) is usually perceived as monotonic and paralleling that of the trivalent lanthanide series. Herein, we present the first extended X-ray absorption fine structure (EXAFS) study performed on a series of aqueous heavy actinide chelates, extending past Cm. The results obtained on diethylenetriaminepentaacetic acid (DTPA) complexes of trivalent Am, Cm, Bk, and Cf show a break to much shorter metal–oxygen nearest-neighbor bond lengths in the case of Cf³⁺. Corroborating those results, density functional theory calculations, extended to Es³⁺, suggest that the shorter Cf–O and Es–O bonds could arise from the departure of the coordinated water molecule and contraction of the ligand around the metal relative to the other [M^IIIDTPA(H₂O)]^2-(M=Am, Cm, Bk) complexes. Taken together, these experimental and theoretical results demonstrate inhomogeneity within the trivalent transplutonium series that has been insinuated and debated in recent years, and that may also be leveraged for future nuclear waste reprocessing technologies.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-06NA25396; AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1477677

Alternate ID(s):: OSTI ID: 1426318; OSTI ID: 1513796

Report Number(s):: LA-UR-17-27807

Journal Information:: Angewandte Chemie (International Edition), Vol. 57, Issue 17; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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