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

Journal Article · · Angewandte Chemie
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]
  1. Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA
  2. Theoretical Division Los Alamos National Laboratory Los Alamos NM 87545 USA
  3. Chemical Sciences Division Lawrence Berkeley National Laboratory Berkeley CA 94720 USA, Department of Nuclear Engineering University of California, Berkeley Berkeley CA 94720 USA
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Abstract The chemistry of trivalent transplutonium ions (Am 3+ , Cm 3+ , Bk 3+ , Cf 3+ , Es 3+ …) 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 Cf 3+ . Corroborating those results, density functional theory calculations, extended to Es 3+ , 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 III DTPA(H 2 O)] 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.

Sponsoring Organization:
USDOE
OSTI ID:
1433275
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 130 Journal Issue: 17; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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