Emergence of californium as the second transitional element in the actinide series

Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E.; Stritzinger, Jared T.; Green, Thomas D.; Diefenbach, Kariem; Cross, Justin N.; Knappenberger, Kenneth L.; Liu, Guokui; Silver, Mark A.; DePrince, A. Eugene; Polinski, Matthew J.; Van Cleve, Shelley M.; House, Jane H.; Kikugawa, Naoki; Gallagher, Andrew; Arico, Alexandra A.; Dixon, David A.; Albrecht-Schmitt, Thomas E.

doi:10.1038/ncomms7827

Title: Emergence of californium as the second transitional element in the actinide series

Journal Article · Thu Apr 16 00:00:00 EDT 2015 · Nature Communications

DOI:https://doi.org/10.1038/ncomms7827· OSTI ID:1225199

Cary, Samantha K. ^[1]; Vasiliu, Monica ^[2]; Baumbach, Ryan E. ^[3]; Stritzinger, Jared T. ^[1]; Green, Thomas D. ^[1]; Diefenbach, Kariem ^[1]; Cross, Justin N. ^[1]; Knappenberger, Kenneth L. ^[1]; Liu, Guokui ^[4]; Silver, Mark A. ^[1]; DePrince, A. Eugene ^[1]; Polinski, Matthew J. ^[1]; Van Cleve, Shelley M. ^[5]; House, Jane H. ^[1]; Kikugawa, Naoki ^[6]; Gallagher, Andrew ^[3]; Arico, Alexandra A. ^[1]; Dixon, David A. ^[2]; Albrecht-Schmitt, Thomas E. ^[1]

Florida State Univ., Tallahassee, FL (United States)
The Univ. of Alabama, Tuscaloosa, AL (United States)
National High Magnetic Field Lab., Tallahassee, FL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
National Institute for Materials Science, Ibaraki (Japan)

A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. Furthermore, the metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; FG02-13ER16414; AC05-00OR22725

OSTI ID:: 1225199

Alternate ID(s):: OSTI ID: 1258660; OSTI ID: 1333650

Journal Information:: Nature Communications, Vol. 6; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 82 works

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References (45)

Crystallography of the compounds of californium—II crystal structure and lattice parameters of californium oxychloride and californium sesquioxide Copeland, J. C.; Cunningham, B. B. Journal of Inorganic and Nuclear Chemistry, Vol. 31, Issue 3 https://doi.org/10.1016/0022-1902(69)80020-5	journal	March 1969
Nobelium: Tracer Chemistry of the Divalent and Trivalent Ions Maly, J.; Sikkeland, T.; Silva, R. Science, Vol. 160, Issue 3832 https://doi.org/10.1126/science.160.3832.1114	journal	June 1968
Structure and magnetic properties of the high- $T_{c}$ related phase ${Cm}_{2} {CuO}_{4}$ Soderholm, L.; Skanthakumar, S.; Williams, C. W. Physical Review B, Vol. 60, Issue 6 https://doi.org/10.1103/PhysRevB.60.4302	journal	August 1999
Covalency effects on the ligand field splittings of octahedral 5f7 compounds Edelstein, N.; Brown, D.; Whittaker, B. Inorganic Chemistry, Vol. 13, Issue 3 https://doi.org/10.1021/ic50133a013	journal	March 1974
A systematic analysis of the spectra of trivalent actinide chlorides in D _{3 h} site symmetry Carnall, William T. The Journal of Chemical Physics, Vol. 96, Issue 12 https://doi.org/10.1063/1.462278	journal	June 1992
The Curium Aqua Ion Skanthakumar, S.; Antonio, Mark R.; Wilson, Richard E. Inorganic Chemistry, Vol. 46, Issue 9 https://doi.org/10.1021/ic061798b	journal	April 2007
In Situ Hydrothermal Reduction of Neptunium(VI) as a Route to Neptunium(IV) Phosphonates Bray, Travis H.; Nelson, Anna-Gay D.; Jin, Geng Bang Inorganic Chemistry, Vol. 46, Issue 26 https://doi.org/10.1021/ic702136h	journal	December 2007
First Structural Determination of a Trivalent Californium Compound with Oxygen Coordination Sykora, Richard E.; Assefa, Zerihun; Haire, Richard G. Inorganic Chemistry, Vol. 45, Issue 2 https://doi.org/10.1021/ic051667v	journal	January 2006
Recent Developments in Synthesis and Structural Chemistry of Nonaqueous Actinide Complexes Jones, Matthew B.; Gaunt, Andrew J. Chemical Reviews, Vol. 113, Issue 2 https://doi.org/10.1021/cr300198m	journal	October 2012
Molrefraktion von Ionen und Molek�len im Lichte der Atomstruktur Fajans, K.; Joos, G. Zeitschrift f�r Physik, Vol. 23, Issue 1 https://doi.org/10.1007/BF01327574	journal	December 1924
[An(H2O)9](CF3SO3)3 (An=U-Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory Apostolidis, Christos; Schimmelpfennig, Bernd; Magnani, Nicola Angewandte Chemie, Vol. 122, Issue 36 https://doi.org/10.1002/ange.201001077	journal	August 2010
Uncovering f-element bonding differences and electronic structure in a series of 1 : 3 and 1 : 4 complexes with a diselenophosphinate ligand Jones, Matthew B.; Gaunt, Andrew J.; Gordon, John C. Chemical Science, Vol. 4, Issue 3 https://doi.org/10.1039/c2sc21806b	journal	January 2013
Struktur und Deformation der Elektronenh�llen in ihrer Bedeutung f�r die chemischen und optischen Eigenschaften anorganischer Verbindungen Fajans, K. Die Naturwissenschaften, Vol. 11, Issue 10 https://doi.org/10.1007/bf01552365	journal	March 1923
Structural investigation of californium under pressure Heathman, S.; Le Bihan, T.; Yagoubi, S. Physical Review B, Vol. 87, Issue 21 https://doi.org/10.1103/physrevb.87.214111	journal	June 2013
Differentiating between Trivalent Lanthanides and Actinides Polinski, Matthew J.; Grant, Daniel J.; Wang, Shuao Journal of the American Chemical Society, Vol. 134, Issue 25 https://doi.org/10.1021/ja303804r	journal	June 2012
Spectroscopic studies and crystal-field analyses of ${Am}^{3 +}$ and ${Eu}^{3 +}$ in the cubic-symmetry site of ${ThO}_{2}$ Hubert, S.; Thouvenot, P.; Edelstein, N. Physical Review B, Vol. 48, Issue 9 https://doi.org/10.1103/PhysRevB.48.5751	journal	September 1993
Magnetic susceptibility of californium ovides Moore, J. R.; Nave, S. E.; Haire, R. G. Journal of the Less Common Metals, Vol. 121 https://doi.org/10.1016/0022-5088(86)90529-1	journal	July 1986
Covalency in f-element complexes Neidig, Michael L.; Clark, David L.; Martin, Richard L. Coordination Chemistry Reviews, Vol. 257, Issue 2 https://doi.org/10.1016/j.ccr.2012.04.029	journal	January 2013
Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning Kaltsoyannis, Nikolas Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic3006025	journal	June 2012
Analysis of the crystal‐field spectra of the actinide tetrafluorides. II. AmF ₄ , CmF ₄ , Cm ⁴⁺ :CeF ₄ , and Bk ⁴⁺ :CeF ₄ Liu, G. K.; Carnall, W. T.; Jursich, G. The Journal of Chemical Physics, Vol. 101, Issue 10 https://doi.org/10.1063/1.468093	journal	November 1994
The Structures and Optical Spectra of Hydrated Transplutonium Ions in the Solid State and in Solution Lindqvist-Reis, Patric; Apostolidis, Christos; Rebizant, Jean Angewandte Chemie International Edition, Vol. 46, Issue 6 https://doi.org/10.1002/anie.200603947	journal	January 2007
An Ion-exchange Study of Possible Hybridized 5f Bonding in the Actinides ¹ Diamond, R. M.; Street, K.; Seaborg, G. T. Journal of the American Chemical Society, Vol. 76, Issue 6 https://doi.org/10.1021/ja01635a001	journal	March 1954
Crystal structure and melting point of californium metal Haire, R. G.; Baybarz, R. D. Journal of Inorganic and Nuclear Chemistry, Vol. 36, Issue 6 https://doi.org/10.1016/0022-1902(74)80067-9	journal	June 1974
Spectroscopic studies and crystal-field analysis of ${Cm}^{3 +}$ and ${Gd}^{3 +}$ in ${LuPO}_{4}$ Sytsma, J.; Murdoch, K. M.; Edelstein, N. M. Physical Review B, Vol. 52, Issue 17 https://doi.org/10.1103/PhysRevB.52.12668	journal	November 1995
Studies on the californium metal system Haire, R. G.; Asprey, L. B. Inorganic and Nuclear Chemistry Letters, Vol. 12, Issue 1 https://doi.org/10.1016/0020-1650(76)80122-5	journal	January 1976
Uranium Tris-aryloxide Derivatives Supported by Triazacyclononane: Engendering a Reactive Uranium(III) Center with a Single Pocket for Reactivity Castro-Rodriguez, Ingrid; Olsen, Kristian; Gantzel, Peter Journal of the American Chemical Society, Vol. 125, Issue 15 https://doi.org/10.1021/ja028342n	journal	April 2003
The Structures and Optical Spectra of Hydrated Transplutonium Ions in the Solid State and in Solution. Lindqvist-Reis, Patric; Apostolidis, Christos; Rebizant, Jean ChemInform, Vol. 38, Issue 16 https://doi.org/10.1002/chin.200716012	journal	April 2007
Preferential extraction of lanthanides over trivalent actinides by monoacidic organophosphates from carboxylic acids and from mixtures of carboxylic and aminopolyacetic acids Weaver, Boyd; Kappelmann, F. A. Journal of Inorganic and Nuclear Chemistry, Vol. 30, Issue 1 https://doi.org/10.1016/0022-1902(68)80089-2	journal	January 1968
First Structural Determination of a Trivalent Californium Compound with Oxygen Coordination. Sykora, Richard E.; Assefa, Zerihun; Haire, Richard G. ChemInform, Vol. 37, Issue 15 https://doi.org/10.1002/chin.200615001	journal	April 2006
[An(H2O)9](CF3SO3)3 (An=U-Cm, Cf): Exploring Their Stability, Structural Chemistry, and Magnetic Behavior by Experiment and Theory Apostolidis, Christos; Schimmelpfennig, Bernd; Magnani, Nicola Angewandte Chemie International Edition, Vol. 49, Issue 36 https://doi.org/10.1002/anie.201001077	journal	June 2010
Californium Haire, Richard G. The Chemistry of the Actinide Elements https://doi.org/10.1007/978-94-009-3155-8_4	book	January 1986
The Structures and Optical Spectra of Hydrated Transplutonium Ions in the Solid State and in Solution Lindqvist-Reis, Patric; Apostolidis, Christos; Rebizant, Jean Angewandte Chemie, Vol. 119, Issue 6 https://doi.org/10.1002/ange.200603947	journal	January 2007
Electron paramagnetic resonance of ${Pu}^{3 +}$ and ${Cf}^{3 +}$ in single crystals of ${LuPO}_{4}$ Kot, W. K.; Edelstein, N. M.; Abraham, M. M. Physical Review B, Vol. 47, Issue 6 https://doi.org/10.1103/PhysRevB.47.3412	journal	February 1993
Unusual structure, bonding and properties in a californium borate Polinski, Matthew J.; Garner, Edward B.; Maurice, Rémi Nature Chemistry, Vol. 6, Issue 5 https://doi.org/10.1038/nchem.1896	journal	March 2014
Solving the Hydration Structure of the Heaviest Actinide Aqua Ion Known: The Californium(III) Case Galbis, Elsa; Hernández-Cobos, Jorge; den Auwer, Christophe Angewandte Chemie, Vol. 122, Issue 22 https://doi.org/10.1002/ange.200906129	journal	April 2010
New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R. Chem. Sci., Vol. 5, Issue 1 https://doi.org/10.1039/C3SC52030G	journal	January 2014
Charge Transfer Vibronic Transitions in Uranyl Tetrachloride Compounds Liu, Guokui; Deifel, Nicholas P.; Cahill, Christopher L. The Journal of Physical Chemistry A, Vol. 116, Issue 2 https://doi.org/10.1021/jp210046j	journal	January 2012
Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds Solomon, Edward I.; Hedman, Britt; Hodgson, Keith O. Coordination Chemistry Reviews, Vol. 249, Issue 1-2 https://doi.org/10.1016/j.ccr.2004.03.020	journal	January 2005
Single-crystal structure validation with the program PLATON Spek, A. L. Journal of Applied Crystallography, Vol. 36, Issue 1, p. 7-13 https://doi.org/10.1107/S0021889802022112	journal	January 2003
Magnetic properties of Dy in Pb2Sr2DyCu3O8 Skanthakumar, S.; Soderholm, L.; Movshovich, R. Journal of Alloys and Compounds, Vol. 303-304 https://doi.org/10.1016/S0925-8388(00)00589-2	journal	May 2000
Solving the Hydration Structure of the Heaviest Actinide Aqua Ion Known: The Californium(III) Case Galbis, Elsa; Hernández-Cobos, Jorge; den Auwer, Christophe Angewandte Chemie International Edition, Vol. 49, Issue 22 https://doi.org/10.1002/anie.200906129	journal	April 2010
Microchemical preparation of tricyclopentadienyl compounds of berkelium, californium, and some lanthanide elements Laubereau, Peter G.; Burns, John H. Inorganic Chemistry, Vol. 9, Issue 5 https://doi.org/10.1021/ic50087a018	journal	May 1970
Selected systematic properties and some recent investigations of actinide metals and alloys Haire, R. G.; Gibson, J. K. Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 143, Issue 1 https://doi.org/10.1007/BF02117545	journal	November 1990
Multiphonon Orbit-Lattice Relaxation in La ${Br}_{3}$ , La ${Cl}_{3}$ , and La $F_{3}$ Riseberg, L. A.; Moos, H. W. Physical Review Letters, Vol. 19, Issue 25 https://doi.org/10.1103/PhysRevLett.19.1423	journal	December 1967
https://doi.org/10.1017/CBO9780511524295.007	book

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