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 = {Thu Feb 22 00:00:00 EST 2018},
month = {Thu Feb 22 00:00:00 EST 2018}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 28 works
Citation information provided by
Web of Science
Web of Science
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.
All figures and tables
(5 total)
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Complexation of Cm( iii ) with the recombinant N-lobe of human serum transferrin studied by time-resolved laser fluorescence spectroscopy (TRLFS)
journal, January 2015
- Bauer, N.; Smith, V. C.; MacGillivray, R. T. A.
- Dalton Transactions, Vol. 44, Issue 4
Structural optimization of molecular clusters with density functional theory combined with basin hopping
journal, October 2012
- Do, Hainam; Besley, Nicholas A.
- The Journal of Chemical Physics, Vol. 137, Issue 13
Speciation of americium in seawater and accumulation in the marine sponge Aplysina cavernicola
journal, January 2015
- Maloubier, Melody; Michel, Hervé; Solari, Pier Lorenzo
- Dalton Transactions, Vol. 44, Issue 47
The Curium Aqua Ion
journal, April 2007
- Skanthakumar, S.; Antonio, Mark R.; Wilson, Richard E.
- Inorganic Chemistry, Vol. 46, Issue 9
A spectrophotometric study of Am( iii ) complexation with nitrate in aqueous solution at elevated temperatures
journal, January 2014
- Tian, Guoxin; Shuh, David K.
- Dalton Trans., Vol. 43, Issue 39
The Chemistry of TALSPEAK: A Review of the Science
journal, December 2014
- Nash, Kenneth L.
- Solvent Extraction and Ion Exchange, Vol. 33, Issue 1
Structural Study of the N,N′ -Dimethylpropyleneurea Solvated Lanthanoid(III) Ions in Solution and Solid State with an Analysis of the Ionic Radii of Lanthanoid(III) Ions
journal, May 2010
- Lundberg, Daniel; Persson, Ingmar; Eriksson, Lars
- Inorganic Chemistry, Vol. 49, Issue 10
Approaching actinide(+III) hydration from first principles
journal, January 2007
- Wiebke, J.; Moritz, A.; Cao, X.
- Phys. Chem. Chem. Phys., Vol. 9, Issue 4
Nine-coordinate rare earth metal complexes with aminopolycarboxylic acids: Mononuclear (NH4)3[TbIII(ttha)]·5H2O and binuclear (NH4)4[Tb 2 III (dtpa)2]·9H2O
journal, January 2008
- Wang, J.; Liu, X. Zh.; Wang, X. F.
- Journal of Structural Chemistry, Vol. 49, Issue 1
Determination of the Hydration Number of Cm(III) in Various Aqueous Solutions
journal, January 1996
- Kimura, Takaumi; Choppin, Gregory R.; Kato, Yoshiharu
- Radiochimica Acta, Vol. 72, Issue 2
Confirmation of standard error analysis techniques applied to EXAFS using simulations
journal, November 2009
- Booth, Corwin H.; Hu, Yung-Jin
- Journal of Physics: Conference Series, Vol. 190
Intramolecular sensitization of americium luminescence in solution: shining light on short-lived forbidden 5f transitions
journal, January 2016
- Sturzbecher-Hoehne, M.; Yang, P.; D'Aléo, A.
- Dalton Transactions, Vol. 45, Issue 24
New Insights into Formation of Trivalent Actinides Complexes with DTPA
journal, November 2012
- Leguay, Sébastien; Vercouter, Thomas; Topin, Sylvain
- Inorganic Chemistry, Vol. 51, Issue 23
Parameter-free calculations of X-ray spectra with FEFF9
journal, January 2010
- Rehr, John J.; Kas, Joshua J.; Vila, Fernando D.
- Physical Chemistry Chemical Physics, Vol. 12, Issue 21
TRLFS study on the complexation of Cm( iii ) and Eu( iii ) with SO 3 -Ph-BTBP
journal, January 2015
- Wagner, Christoph; Müllich, Udo; Geist, Andreas
- Dalton Transactions, Vol. 44, Issue 39
Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state
journal, August 2016
- Silver, M. A.; Cary, S. K.; Johnson, J. A.
- Science, Vol. 353, Issue 6302
Complexation thermodynamics and structural studies of trivalent actinide and lanthanide complexes with DTPA, MS-325 and HMDTPA
journal, April 2013
- Thakur, Punam; Conca, James L.; Dodge, Cleveland J.
- Radiochimica Acta, Vol. 101, Issue 4
Theoretical insights into covalency driven f element separations
journal, January 2013
- Roy, Lindsay E.; Bridges, Nicholas J.; Martin, Leigh R.
- Dalton Trans., Vol. 42, Issue 7
Berkelium redox speciation
journal, January 2002
- Antonio, M. R.; Williams, C. W.; Soderholm, L.
- Radiochimica Acta, Vol. 90, Issue 12
X-ray-absorption fine-structure standards: A comparison of experiment and theory
journal, September 1995
- Li, G. G.; Bridges, F.; Booth, C. H.
- Physical Review B, Vol. 52, Issue 9
Alternatives to HDEHP and DTPA for Simplified TALSPEAK Separations
journal, June 2011
- Braley, Jenifer C.; Grimes, Travis S.; Nash, Kenneth L.
- Industrial & Engineering Chemistry Research, Vol. 51, Issue 2
Emergence of californium as the second transitional element in the actinide series
journal, April 2015
- Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E.
- Nature Communications, Vol. 6, Issue 1
First Investigation on the L Edges of the 249 Cf Aquo Ion by X-ray Absorption Spectroscopy
journal, September 1999
- Revel, R.; Den Auwer, C.; Madic, C.
- Inorganic Chemistry, Vol. 38, Issue 18
The syntheses of lanthanide metal complexes with diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid and the comparison of their crystal structures
journal, March 2003
- Inomata, Yoshie; Sunakawa, Takako; Howell, Frank Scott
- Journal of Molecular Structure, Vol. 648, Issue 1-2
Sorption of trivalent lanthanides and actinides onto montmorillonite: Macroscopic, thermodynamic and structural evidence for ternary hydroxo and carbonato surface complexes on multiple sorption sites
journal, August 2016
- Fernandes, M. Marques; Scheinost, A. C.; Baeyens, B.
- Water Research, Vol. 99
On the Origin of Covalent Bonding in Heavy Actinides
journal, July 2017
- Kelley, Morgan P.; Su, Jing; Urban, Matthew
- Journal of the American Chemical Society, Vol. 139, Issue 29
Number of relevant independent points in x-ray-absorption fine-structure spectra
journal, October 1993
- Stern, Edward A.
- Physical Review B, Vol. 48, Issue 13
Structural and Thermodynamic Properties of the Cm III Ion Solvated by Water and Methanol
journal, April 2016
- Kelley, Morgan P.; Yang, Ping; Clark, Sue B.
- Inorganic Chemistry, Vol. 55, Issue 10
Binuclear structure in the ammonium salt of gadolinium(III) diethylenetriaminepentaacetate, (NH4)4[Gd2(DTPA)2]·6H2O
journal, April 1995
- Inoue, Michiko B.; Inoue, Motomichi; Fernando, Quintus
- Inorganica Chimica Acta, Vol. 232, Issue 1-2
Coordination Chemistry of Trivalent Lanthanide and Actinide Ions in Dilute and Concentrated Chloride Solutions
journal, February 2000
- Allen, P. G.; Bucher, J. J.; Shuh, D. K.
- Inorganic Chemistry, Vol. 39, Issue 3
Actinide oxalates, solid state structures and applications
journal, May 2014
- Abraham, Francis; Arab-Chapelet, Bénédicte; Rivenet, Murielle
- Coordination Chemistry Reviews, Vol. 266-267
Temperature and pH Dependence XAFS Study of Gd(DOTA) - and Gd(DTPA) 2 - Complexes: Solid State and Solution Structures
journal, July 1998
- Bénazeth, Simone; Purans, Juris; Chalbot, Marie-Cécile
- Inorganic Chemistry, Vol. 37, Issue 15
Optimized Relaxivity and Stability of [Gd(H(2,2)-1,2-HOPO)(H 2 O)] - for Use as an MRI Contrast Agent 1
journal, June 2007
- Jocher, Christoph J.; Botta, Mauro; Avedano, Stefano
- Inorganic Chemistry, Vol. 46, Issue 12
Optical spectroscopy of neodymium(III) complexes with diethylenetriaminepentaacetic acid in solution and in [C(NH2)3]2[Nd(dtpa)(H2O)]·7H2O single crystal
journal, April 2000
- Mondry, Anna; Starynowicz, Azemysław
- Polyhedron, Vol. 19, Issue 7
Syntheses and crystal structures of nine-coordinate K2[EuIII(dtpa)(H2O)]·5H2O and Na2[TbIII(Httha)]·6H2O complexes
journal, October 2009
- Liu, B.; Wang, Y. F.; Wang, J.
- Journal of Structural Chemistry, Vol. 50, Issue 5
Solving the Hydration Structure of the Heaviest Actinide Aqua Ion Known: The Californium(III) Case
journal, April 2010
- Galbis, Elsa; Hernández-Cobos, Jorge; den Auwer, Christophe
- Angewandte Chemie, Vol. 122, Issue 22
Synthesis and structural determination of binuclear nine-coordinate (NH4)4[Yb2(dtpa)2]·9H2O
journal, August 2002
- Wang, Jun; Zhang, Xiang-Dong; Liu, Zhen-Rong
- Journal of Molecular Structure, Vol. 613, Issue 1-3
Syntheses and structural determinations of the nine-coordinate rare earth metal: Na 4 [Dy III (dtpa)(H 2 O)] 2 ·16H 2 O, Na[Dy III (edta)(H 2 O) 3 ]·3.25H 2 O and Na 3 [Dy III (nta) 2 (H 2 O)]·5.5H 2 O
journal, October 2007
- Wang, Jun; Gao, Guangrui; Zhang, Zhaohong
- Journal of Coordination Chemistry, Vol. 60, Issue 20
Solving the Hydration Structure of the Heaviest Actinide Aqua Ion Known: The Californium(III) Case
journal, April 2010
- Galbis, Elsa; Hernández-Cobos, Jorge; den Auwer, Christophe
- Angewandte Chemie International Edition, Vol. 49, Issue 22
Separation of actinides from spent nuclear fuel: A review
journal, November 2016
- Veliscek-Carolan, Jessica
- Journal of Hazardous Materials, Vol. 318
Covalency in Americium(III) Hexachloride
journal, June 2017
- Cross, Justin N.; Su, Jing; Batista, Enrique R.
- Journal of the American Chemical Society, Vol. 139, Issue 25
An EXAFS and TRLFS study of the sorption of trivalent actinides onto smectite and kaolinite
journal, January 2004
- Stumpf, Thorsten; Hennig, C.; Bauer, A.
- Radiochimica Acta, Vol. 92, Issue 3
X-ray-absorption fine structure in embedded atoms
journal, May 1994
- Rehr, J. J.; Booth, C. H.; Bridges, F.
- Physical Review B, Vol. 49, Issue 17
Sensitizing Curium Luminescence through an Antenna Protein To Investigate Biological Actinide Transport Mechanisms
journal, February 2013
- Sturzbecher-Hoehne, Manuel; Goujon, Christophe; Deblonde, Gauthier J. -P.
- Journal of the American Chemical Society, Vol. 135, Issue 7
Complexation of Curium(III) with DTPA at 10–70 °C: Comparison with Eu(III)–DTPA in Thermodynamics, Luminescence, and Coordination Modes
journal, January 2015
- Tian, Guoxin; Zhang, Zhiyong; Martin, Leigh R.
- Inorganic Chemistry, Vol. 54, Issue 4
The size of actinoid(III) ions – structural analysis vs. common misinterpretations
journal, July 2016
- Lundberg, Daniel; Persson, Ingmar
- Coordination Chemistry Reviews, Vol. 318
Syntheses and structural determination of binuclear nine-coordinate (NH 4 ) 4 [Sm III 2 (Httha) 2 ]·16H 2 O and 2-D ladder-like binuclear nine-coordinate (NH 4 ) 4 [Sm III 2 (dtpa) 2 ]·10H 2 O
journal, February 2014
- Ma, Congcong; Li, Ying; Wang, Jun
- Journal of Coordination Chemistry, Vol. 67, Issue 4
A review of the demonstration of innovative solvent extraction processes for the recovery of trivalent minor actinides from PUREX raffinate
journal, August 2012
- Modolo, Giuseppe; Wilden, A.; Geist, Andreas
- Radiochimica Acta, Vol. 100, Issue 8-9
Chelation and stabilization of berkelium in oxidation state +IV
journal, April 2017
- Deblonde, Gauthier J. -P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.
- Nature Chemistry, Vol. 9, Issue 9
Approaching Actinide(+III) Hydration from First Principles
journal, May 2007
- Wiebke, J.; Moritz, A.; Cao, X.
- ChemInform, Vol. 38, Issue 18
Complexation of Cm(III) with the recombinant N-lobe of human serum transferrin studied by time-resolved laser fluorescence spectroscopy (TRLFS)
text, January 2015
- Bauer, N.; Smith, V. C.; MacGillivray, R. T. A.
- Karlsruhe
X-ray Absorption Fine Structure in Embedded Atoms
text, January 1994
- Rehr, J. J.; Booth, C. H.; Bridges, F.
- arXiv
Works referencing / citing this record:
Contemporary Chemistry of Berkelium and Californium
journal, June 2019
- White, Frankie D.; Dan, David; Albrecht‐Schmitt, Thomas E.
- Chemistry – A European Journal, Vol. 25, Issue 44
Ultra-selective ligand-driven separation of strategic actinides
journal, June 2019
- Deblonde, Gauthier J. -P.; Ricano, Abel; Abergel, Rebecca J.
- Nature Communications, Vol. 10, Issue 1
Ultra-selective ligand-driven separation of strategic actinides
journal, June 2019
- Deblonde, Gauthier J. -P.; Ricano, Abel; Abergel, Rebecca J.
- Nature Communications, Vol. 10, Issue 1
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.