Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series
Abstract
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 [MIIIDTPA(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.
- Authors:
-
[1];
[2];
[2];
[2];
[1];
[3]
- 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
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1477677
- Alternate Identifier(s):
- OSTI ID: 1426318; OSTI ID: 1513796
- Report Number(s):
- LA-UR-17-27807
Journal ID: ISSN 1433-7851
- Grant/Contract Number:
- AC52-06NA25396; AC02-05CH11231; AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 17; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; actinides; berkelium; californium; chelates; EXAFS spectroscopy
Citation Formats
Deblonde, Gauthier J. -P., Kelley, Morgan P., Su, Jing, Batista, Enrique R., Yang, Ping, Booth, Corwin H., and Abergel, Rebecca J.. Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series. United States: N. p., 2018.
Web. doi:10.1002/anie.201709183.
Deblonde, Gauthier J. -P., Kelley, Morgan P., Su, Jing, Batista, Enrique R., Yang, Ping, Booth, Corwin H., & Abergel, Rebecca J.. Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series. United States. https://doi.org/10.1002/anie.201709183
Deblonde, Gauthier J. -P., Kelley, Morgan P., Su, Jing, Batista, Enrique R., Yang, Ping, Booth, Corwin H., and Abergel, Rebecca J.. Thu .
"Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series". United States. https://doi.org/10.1002/anie.201709183. https://www.osti.gov/servlets/purl/1477677.
@article{osti_1477677,
title = {Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series},
author = {Deblonde, Gauthier J. -P. and Kelley, Morgan P. and Su, Jing and Batista, Enrique R. and Yang, Ping and Booth, Corwin H. and Abergel, Rebecca J.},
abstractNote = {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 [MIIIDTPA(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.},
doi = {10.1002/anie.201709183},
journal = {Angewandte Chemie (International Edition)},
number = 17,
volume = 57,
place = {United States},
year = {2018},
month = {2}
}
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Figures / Tables:
Scheme 1: Left: structure of H5DTPA. Right: [AnIIIDTPA]2- complex, with coordinating atoms represented as balls and all others as sticks. Hydrogen atoms are hidden for clarity.
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