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

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. 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 IIIDTPA(H 2O)] 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:
ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [2] ;  [2] ; ORCiD logo [2] ; ORCiD logo [1] ; ORCiD logo [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. 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:
Report Number(s):
LA-UR-17-27807
Journal ID: ISSN 1433-7851
Grant/Contract Number:
AC52-06NA25396; AC02-05CH11231; AC02-76SF00515
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
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; actinides; berkelium; californium; chelates; EXAFS spectroscopy
OSTI Identifier:
1477677
Alternate Identifier(s):
OSTI ID: 1426318

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., 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. doi: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.. 2018. "Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series". United States. doi:10.1002/anie.201709183.
@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. 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}
}