Uncovering the Origin of Divergence in the CsM(CrO 4 ) 2 (M = La, Pr, Nd, Sm, Eu; Am) Family through Examination of the Chemical Bonding in a Molecular Cluster and by Band Structure Analysis

Galley, Shane S.; Arico, Alexandra A.; Lee, Tsung-Han; Deng, Xiaoyu; Yao, Yong-Xin; Sperling, Joseph M.; Proust, Vanessa; Storbeck, Julia S.; Dobrosavljevic, Vladimir; Neu, Jennifer N.; Siegrist, Theo; Baumbach, Ryan E.; Albrecht-Schmitt, Thomas E.; Kaltsoyannis, Nikolas; Lanatà, Nicola

doi:10.1021/jacs.7b09474

Title: Uncovering the Origin of Divergence in the CsM(CrO ₄ ) ₂ (M = La, Pr, Nd, Sm, Eu; Am) Family through Examination of the Chemical Bonding in a Molecular Cluster and by Band Structure Analysis

Journal Article · Wed Jan 10 00:00:00 EST 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b09474· OSTI ID:1434561

Galley, Shane S. ^[1]; Arico, Alexandra A. ^[1]; Lee, Tsung-Han ^[2]; Deng, Xiaoyu ^[2];

^[3]; Sperling, Joseph M. ^[1]; Proust, Vanessa ^[1]; Storbeck, Julia S. ^[1]; Dobrosavljevic, Vladimir ^[4]; Neu, Jennifer N. ^[5]; Siegrist, Theo ^[5]; Baumbach, Ryan E. ^[6];

^[1];

^[7]; Lanatà, Nicola ^[6]

Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
Department of Physics and Astronomy, Rutgers University, Piscataway, New Jersey 08856-8019, United States
Department of Physics and Astronomy, and Ames Laboratory, U.S. Department of Energy, Iowa State University, Ames, Iowa 50011, United States
Department of Physics, Florida State University, Tallahassee, Florida 32306, United States, National High Magnetic Field Laboratory, Tallahassee, Florida 32310, United States
National High Magnetic Field Laboratory, Tallahassee, Florida 32310, United States, Department of Chemical Engineering, Florida State University, Tallahassee, Florida 32310, United States
National High Magnetic Field Laboratory, Tallahassee, Florida 32310, United States
School of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, United Kingdom

A series of f-block chromates, CsM(CrO₄)₂ (M = La, Pr, Nd, Sm, Eu; Am), were prepared revealing notable differences between the Am^III derivatives and their lanthanide analogs. While all compounds form similar layered structures, the americium compound exhibits polymorphism and adopts both a structure isomorphous with the early lanthanides as well as one that possesses lower symmetry. Both polymorphs are dark red and possess band gaps that are smaller than the Ln^III compounds. In order to probe the origin of these differences, the electronic structure of α-CsSm(CrO₄)₂, α-CsEu(CrO₄)₂, and α-CsAm(CrO₄)₂ were studied using both a molecular cluster approach featuring hybrid density functional theory and QTAIM analysis and by the periodic LDA+GA and LDA+DMFT methods. Notably, the covalent contributions to bonding by the f orbitals were found to be more than twice as large in the Am^III chromate than in the Sm^III and Eu^III compounds, and even larger in magnitude than the Am-5f spin–orbit splitting in this system. Our analysis indicates also that the Am–O covalency in α-CsAm(CrO₄)₂ is driven by the degeneracy of the 5f and 2p orbitals, and not by orbital overlap.

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Research Organization:: Ames Lab., Ames, IA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST)

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

Grant/Contract Number:: SC0016568; AC02-07CH11358

OSTI ID:: 1434561

Alternate ID(s):: OSTI ID: 1427725; OSTI ID: 1508589

Report Number(s):: IS-J-9584

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 140 Journal Issue: 5; ISSN 0002-7863

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 12 works

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References (100)

Covalency in AnCp4 (An = Th–Cm): a comparison of molecular orbital, natural population and atoms-in-molecules analyses Tassell, Matthew J.; Kaltsoyannis, Nikolas Dalton Transactions, Vol. 39, Issue 29 https://doi.org/10.1039/c000704h	journal	January 2010
Syntheses, Structures, and Spectroscopic Properties of Plutonium and Americium Phosphites and the Redetermination of the Ionic Radii of Pu(III) and Am(III) Cross, Justin N.; Villa, Eric M.; Wang, Shuao Inorganic Chemistry, Vol. 51, Issue 15 https://doi.org/10.1021/ic300958z	journal	July 2012
Synthesis and Characterization of f -Element Iodate Architectures with Variable Dimensionality, α- and β-Am(IO ₃ ) ₃ Runde, Wolfgang; Bean, Amanda C.; Brodnax, Lia F. Inorganic Chemistry, Vol. 45, Issue 6 https://doi.org/10.1021/ic0516414	journal	March 2006
From Yellow to Black: Dramatic Changes between Cerium(IV) and Plutonium(IV) Molybdates Cross, Justin N.; Duncan, Patrick M.; Villa, Eric M. Journal of the American Chemical Society, Vol. 135, Issue 7 https://doi.org/10.1021/ja311910h	journal	February 2013
Bis(cyclooctatetraenyl)neptunium(IV) and bis(cyclooctatetraenyl)plutonium(IV) Karraker, David G.; Stone, John Austin.; Jones, Erwin Rudolph. Journal of the American Chemical Society, Vol. 92, Issue 16 https://doi.org/10.1021/ja00719a014	journal	August 1970
Transition metal iodates. V. Preparation and characterization of the smaller lanthanide iodates Nassau, K.; Shiever, J. W.; Prescott, B. E. Journal of Solid State Chemistry, Vol. 11, Issue 4 https://doi.org/10.1016/S0022-4596(74)80036-8	journal	December 1974
Covalency hinders AnO ₂ (H ₂ O) ⁺ → AnO(OH) ₂ ⁺ isomerisation (An = Pa–Pu) Kaltsoyannis, Nikolas Dalton Transactions, Vol. 45, Issue 7 https://doi.org/10.1039/C5DT04317D	journal	January 2016
Determining Relative f and d Orbital Contributions to M–Cl Covalency in MCl ₆ ^2– (M = Ti, Zr, Hf, U) and UOCl ₅ ^– Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R. Journal of the American Chemical Society, Vol. 134, Issue 12 https://doi.org/10.1021/ja2105015	journal	March 2012
Organometallic neptunium(III) complexes Dutkiewicz, Michał S.; Farnaby, Joy H.; Apostolidis, Christos Nature Chemistry, Vol. 8, Issue 8 https://doi.org/10.1038/nchem.2520	journal	May 2016
Transition metal iodates. VI. Preparation and characterization of the larger lanthanide iodates Nassau, K.; Shiever, J. W.; Prescott, B. E. Journal of Solid State Chemistry, Vol. 14, Issue 2 https://doi.org/10.1016/0022-4596(75)90002-X	journal	June 1975
Identification of the Formal +2 Oxidation State of Plutonium: Synthesis and Characterization of {Pu ^II [C ₅ H ₃ (SiMe ₃ ) ₂ ] ₃ } ⁻ Windorff, Cory J.; Chen, Guo P.; Cross, Justin N. Journal of the American Chemical Society, Vol. 139, Issue 11 https://doi.org/10.1021/jacs.7b00706	journal	March 2017
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
Does covalency really increase across the 5f series? A comparison of molecular orbital, natural population, spin and electron density analyses of AnCp ₃ (An = Th–Cm; Cp = η ⁵ -C ₅ H ₅ ) Kirker, Ian; Kaltsoyannis, Nikolas Dalton Trans., Vol. 40, Issue 1 https://doi.org/10.1039/C0DT01018A	journal	January 2011
Emergence of comparable covalency in isostructural cerium( iv )– and uranium( iv )–carbon multiple bonds Gregson, Matthew; Lu, Erli; Tuna, Floriana Chemical Science, Vol. 7, Issue 5 https://doi.org/10.1039/C6SC00278A	journal	January 2016
Unprecedented Bidentate Coordination of the Uranyl Cation by the Chromate Anion in the Structure of [(CH3)2CHNH3]2[UO2(CrO4)2] Siidra, Oleg I.; Nazarchuk, Evgeny V.; Krivovichev, Sergey V. European Journal of Inorganic Chemistry, Vol. 2012, Issue 2 https://doi.org/10.1002/ejic.201101192	journal	December 2011
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
Incipient class II mixed valency in a plutonium solid-state compound Cary, Samantha K.; Galley, Shane S.; Marsh, Matthew L. Nature Chemistry, Vol. 9, Issue 9 https://doi.org/10.1038/nchem.2777	journal	May 2017
Emergence of californium as the second transitional element in the actinide series Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7827	journal	April 2015
Thorium(IV) chromate(VI) monohydrate Sullens, Tyler A.; Albrecht-Schmitt, Thomas E. Acta Crystallographica Section E Structure Reports Online, Vol. 62, Issue 12 https://doi.org/10.1107/S1600536806047416	journal	November 2006
Synthesis and crystal structure of americium(V) dichromate, Cs3AmO2(Cr2O7)2·H2O Charushnikova, I. A.; Fedoseev, A. M. Radiochemistry, Vol. 55, Issue 1 https://doi.org/10.1134/S1066362213010037	journal	January 2013
Surprising Coordination Geometry Differences in CeIV- and PuIV-Maltol Complexes Szigethy, Géza; Xu, Jide; Gorden, Anne E. V. European Journal of Inorganic Chemistry, Vol. 2008, Issue 13 https://doi.org/10.1002/ejic.200800144	journal	May 2008
SHELXT – Integrated space-group and crystal-structure determination Sheldrick, George M. Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8 https://doi.org/10.1107/S2053273314026370	journal	January 2015
On the Origin of Covalent Bonding in Heavy Actinides Kelley, Morgan P.; Su, Jing; Urban, Matthew Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b03251	journal	July 2017
Completing the Series of +2 Ions for the Lanthanide Elements: Synthesis of Molecular Complexes of Pr ²⁺ , Gd ²⁺ , Tb ²⁺ , and Lu ²⁺ MacDonald, Matthew R.; Bates, Jefferson E.; Ziller, Joseph W. Journal of the American Chemical Society, Vol. 135, Issue 26 https://doi.org/10.1021/ja403753j	journal	May 2013
Thermodynamic Study of the Complexation of Trivalent Actinide and Lanthanide Cations by ADPTZ, a Tridentate N-Donor Ligand Miguirditchian, Manuel; Guillaneux, Denis; Guillaumont, Dominique Inorganic Chemistry, Vol. 44, Issue 5 https://doi.org/10.1021/ic0488785	journal	March 2005
Electron-transfer and f-d absorption bands of some lanthanide and actinide complexes and the standard (II-III) oxidation potential for each member of the lanthanide and actinide series Nugent, L. J.; Baybarz, R. D.; Burnett, J. L. The Journal of Physical Chemistry, Vol. 77, Issue 12 https://doi.org/10.1021/j100631a011	journal	June 1973
Slave Boson Theory of Orbital Differentiation with Crystal Field Effects: Application to ${UO}_{2}$ Lanatà, Nicola; Yao, Yongxin; Deng, Xiaoyu Physical Review Letters, Vol. 118, Issue 12 https://doi.org/10.1103/PhysRevLett.118.126401	journal	March 2017
Synthesis and Initial Evaluation for In Vivo Chelation of Pu(IV) of a Mixed Octadentate Spermine-Based Ligand Containing 4-Carbamoyl-3-hydroxy-1-methyl-2(1 H )-pyridinone and 6-Carbamoyl-1-hydroxy-2(1 H )-pyridinone Xu, Jide; Durbin, Patricia W.; Kullgren, Birgitta Journal of Medicinal Chemistry, Vol. 45, Issue 18 https://doi.org/10.1021/jm010564t	journal	August 2002
Local Structure in Americium and Californium Hexacyanoferrates - Comparison with Their Lanthanide Analogues Dupouy, Gaelle; Bonhoure, Isabelle; Conradson, Steven D. European Journal of Inorganic Chemistry, Vol. 2011, Issue 10 https://doi.org/10.1002/ejic.201001004	journal	February 2011
Highly Kinked Uranyl Chromate Nitrate Layers in the Crystal Structures of A[(UO2)(CrO4)(NO3)] (A = K, Rb) Siidra, Oleg I.; Nazarchuk, Evgeny V.; Krivovichev, Sergey V. Zeitschrift für anorganische und allgemeine Chemie, Vol. 638, Issue 6 https://doi.org/10.1002/zaac.201200009	journal	March 2012
Synthesis, crystallographic data, magnetic properties and vibrational study of the new series KLn(CrO4)4 (Ln = Eu, Gd, Tb) Bueno, I.; Parada, C.; Puche, R. Saez Journal of Physics and Chemistry of Solids, Vol. 51, Issue 9 https://doi.org/10.1016/0022-3697(90)90073-O	journal	January 1990
Selective Extraction of Americium(III) over Europium(III) with the Pyridylpyrazole Based Tetradentate Ligands: Experimental and Theoretical Study Wang, Jieru; Su, Dongping; Wang, Dongqi Inorganic Chemistry, Vol. 54, Issue 22 https://doi.org/10.1021/acs.inorgchem.5b01452	journal	October 2015
Synthesis and characterization of β-RbSc(CrO4)2 Melnikov, P.; Ferracin, L. C. Journal of Alloys and Compounds, Vol. 224, Issue 2 https://doi.org/10.1016/0925-8388(95)01588-4	journal	July 1995
Spectroscopic Properties of Rare Earths Wybourne, Brian G.; Meggers, William F. Physics Today, Vol. 18, Issue 9 https://doi.org/10.1063/1.3047727	journal	September 1965
Superconductivity of Americium Smith, J. L.; Haire, R. G. Science, Vol. 200, Issue 4341 https://doi.org/10.1126/science.200.4341.535	journal	May 1978
The valence-fluctuating ground state of plutonium Janoschek, Marc; Das, Pinaki; Chakrabarti, Bismayan Science Advances, Vol. 1, Issue 6 https://doi.org/10.1126/sciadv.1500188	journal	July 2015
Covalency-Driven Dimerization of Plutonium(IV) in a Hydroxamate Complex Silver, Mark A.; Cary, Samantha K.; Stritzinger, Jared T. Inorganic Chemistry, Vol. 55, Issue 11 https://doi.org/10.1021/acs.inorgchem.6b00340	journal	May 2016
Plutonium(IV) Sequestration: Structural and Thermodynamic Evaluation of the Extraordinarily Stable Cerium(IV) Hydroxypyridinonate Complexes¹ Xu, Jide; Radkov, Emil; Ziegler, Marco Inorganic Chemistry, Vol. 39, Issue 18, p. 4156-4164 https://doi.org/10.1021/ic000063i	journal	September 2000
Hydrothermal synthesis, structure, Raman spectroscopy, and self-irradiation studies of 248Cm(IO3)3 Sykora, Richard E.; Assefa, Zerihun; Haire, Richard G. Journal of Solid State Chemistry, Vol. 177, Issue 12 https://doi.org/10.1016/j.jssc.2004.09.015	journal	December 2004
Isopropylammonium Layered Uranyl Chromates: Syntheses and Crystal Structures of [(CH3)2CHNH3]3[(UO2)3(CrO4)2O(OH)3] and[(CH3)2CHNH3]2[(UO2)2(CrO4)3(H2O)] Siidra, Oleg I.; Nazarchuk, Evgeny V.; Krivovichev, Sergey V. Zeitschrift für anorganische und allgemeine Chemie, Vol. 638, Issue 6 https://doi.org/10.1002/zaac.201100558	journal	March 2012
Structural Periodicity in Plutonium(IV) Sulfates Wilson, Richard E. Inorganic Chemistry, Vol. 50, Issue 12 https://doi.org/10.1021/ic200384h	journal	June 2011
Hydrothermal Synthesis of Rare Earth Iodates from the Corresponding Periodates: II1). Synthesis and Structures of Ln(IO3)3 (Ln = Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er) and Ln(IO3)3· 2H2O (Ln = Eu, Gd, Dy, Er, Tm, Yb) Douglas, Paul; Hector, Andrew L.; Levason, William Zeitschrift für anorganische und allgemeine Chemie, Vol. 630, Issue 3 https://doi.org/10.1002/zaac.200300377	journal	March 2004
Comparisons of Pu(IV) and Ce(IV) Diphosphonates Diwu, Juan; Nelson, Anna-Gay D.; Wang, Shuao Inorganic Chemistry, Vol. 49, Issue 7 https://doi.org/10.1021/ic100184q	journal	April 2010
A study of ionic conductivity in double rare-earth chromates Melnikov, P.; Bueno, I.; Parada, C. Solid State Ionics, Vol. 63-65 https://doi.org/10.1016/0167-2738(93)90162-V	journal	September 1993
Crystal chemistry of thorium nitrates and chromates Sigmon, Ginger E.; Burns, Peter C. Journal of Solid State Chemistry, Vol. 183, Issue 7 https://doi.org/10.1016/j.jssc.2010.04.042	journal	July 2010
Valence basis sets for relativistic energy-consistent small-core actinide pseudopotentials Cao, Xiaoyan; Dolg, Michael; Stoll, Hermann The Journal of Chemical Physics, Vol. 118, Issue 2 https://doi.org/10.1063/1.1521431	journal	January 2003
Transition metal iodates. VII. Crystallographic and nonlinear optic survey of the 4f-iodates Abrahams, S. C.; Bernstein, J. L.; Nassau, K. Journal of Solid State Chemistry, Vol. 16, Issue 1-2 https://doi.org/10.1016/0022-4596(76)90020-7	journal	January 1976
Relevance of Kondo physics for the temperature dependence of the bulk modulus in plutonium Janoschek, Marc; Lander, Gerry; Lawrence, Jon M. Proceedings of the National Academy of Sciences, Vol. 114, Issue 3 https://doi.org/10.1073/pnas.1618967114	journal	January 2017
Segmented contraction scheme for small-core actinide pseudopotential basis sets Cao, Xiaoyan; Dolg, Michael Journal of Molecular Structure: THEOCHEM, Vol. 673, Issue 1-3 https://doi.org/10.1016/j.theochem.2003.12.015	journal	March 2004
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
Measurement of the first ionization potential of lawrencium, element 103 Sato, T. K.; Asai, M.; Borschevsky, A. Nature, Vol. 520, Issue 7546 https://doi.org/10.1038/nature14342	journal	April 2015
Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism Gunnarsson, O.; Lundqvist, B. I. Physical Review B, Vol. 13, Issue 10 https://doi.org/10.1103/PhysRevB.13.4274	journal	May 1976
Hydrothermal Synthesis of Rare Earth Iodates from the Corresponding Periodates: Structures of Sc(IO3)3, Y(IO3)3 · 2 H2O, La(IO3)3 · 1/2 H2O and Lu(IO3)3 · 2 H2O Hector, Andrew L.; Henderson, Stuart J.; Levason, William Zeitschrift für anorganische und allgemeine Chemie, Vol. 628, Issue 1 https://doi.org/10.1002/1521-3749(200201)628:1<198::AID-ZAAC198>3.0.CO;2-L	journal	January 2002
Crystal growth, structure, and properties of KLa(CrO ₄ ) ₂ Bueno, Isabel; Parada, Carmen; García, Oscar J. Chem. Soc., Dalton Trans., Issue 7 https://doi.org/10.1039/DT9880001911	journal	January 1988
Quantifying the σ and π Interactions between U(V) f Orbitals and Halide, Alkyl, Alkoxide, Amide and Ketimide Ligands Lukens, Wayne W.; Edelstein, Norman M.; Magnani, Nicola Journal of the American Chemical Society, Vol. 135, Issue 29 https://doi.org/10.1021/ja403815h	journal	July 2013
New Insights into Formation of Trivalent Actinides Complexes with DTPA Leguay, Sébastien; Vercouter, Thomas; Topin, Sylvain Inorganic Chemistry, Vol. 51, Issue 23 https://doi.org/10.1021/ic3011019	journal	November 2012
First-principles calculations of the electronic structure and spectra of strongly correlated systems: dynamical mean-field theory Anisimov, V. I.; Poteryaev, A. I.; Korotin, M. A. Journal of Physics: Condensed Matter, Vol. 9, Issue 35 https://doi.org/10.1088/0953-8984/9/35/010	journal	September 1997
Structural, Spectroscopic, and Theoretical Comparison of Traditional vs Recently Discovered Ln ²⁺ Ions in the [K(2.2.2-cryptand)][(C ₅ H ₄ SiMe ₃ ) ₃ Ln] Complexes: The Variable Nature of Dy ²⁺ and Nd ²⁺ Fieser, Megan E.; MacDonald, Matthew R.; Krull, Brandon T. Journal of the American Chemical Society, Vol. 137, Issue 1 https://doi.org/10.1021/ja510831n	journal	December 2014
Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state Silver, M. A.; Cary, S. K.; Johnson, J. A. Science, Vol. 353, Issue 6302 https://doi.org/10.1126/science.aaf3762	journal	August 2016
On rubidium lanthanide double chromates Melnikov, P.; Parada, C.; Bueno, I. Journal of Alloys and Compounds, Vol. 190, Issue 2 https://doi.org/10.1016/0925-8388(93)90409-G	journal	January 1993
Expanding the Chemistry of Molecular U ²⁺ Complexes: Synthesis, Characterization, and Reactivity of the {[C ₅ H ₃ (SiMe ₃ ) ₂ ] ₃ U} ⁻ Anion Windorff, Cory J.; MacDonald, Matthew R.; Meihaus, Katie R. Chemistry - A European Journal, Vol. 22, Issue 2 https://doi.org/10.1002/chem.201503583	journal	December 2015
Bonding Changes in Plutonium(III) and Americium(III) Borates Polinski, Matthew J.; Wang, Shuao; Alekseev, Evgeny V. Angewandte Chemie International Edition, Vol. 50, Issue 38 https://doi.org/10.1002/anie.201103502	journal	August 2011
Paramagnetism of Aqueous Actinide Cations. Part I: Perchloric Acid Media Wall, Thomas F.; Jan, Steve; Autillo, Matthieu Inorganic Chemistry, Vol. 53, Issue 5 https://doi.org/10.1021/ic402371x	journal	February 2014
Monomers, Dimers, and Helices: Complexities of Cerium and Plutonium Phenanthrolinecarboxylates Cary, Samantha K.; Ferrier, Maryline G.; Baumbach, Ryan E. Inorganic Chemistry, Vol. 55, Issue 9 https://doi.org/10.1021/acs.inorgchem.6b00077	journal	April 2016
The accuracy of the pseudopotential approximation: non-frozen-core effects for spectroscopic constants of alkali fluorides XF (X = K, Rb, Cs) Leininger, Thierry; Nicklass, Andreas; Küchle, Wolfgang Chemical Physics Letters, Vol. 255, Issue 4-6 https://doi.org/10.1016/0009-2614(96)00382-X	journal	June 1996
Crystal growth, IR and Raman spectra, thermal decomposition and magnetic properties of KLn(CrO4)2 (Ln ≡ Pr, Nd, Sm) Bueno, I.; Garcia, O.; Parada, C. Journal of the Less Common Metals, Vol. 139, Issue 2 https://doi.org/10.1016/0022-5088(88)90007-0	journal	May 1988
The First Sodium Uranyl Chromate, Na4[(UO2)(CrO4)3]: Synthesis and Crystal Structure Determination Krivovichev, Sergey V.; Burns, Peter C. Zeitschrift für anorganische und allgemeine Chemie, Vol. 629, Issue 11 https://doi.org/10.1002/zaac.200300109	journal	October 2003
Principle of Maximum Entanglement Entropy and Local Physics of Strongly Correlated Materials Lanatà, Nicola; Strand, Hugo U. R.; Yao, Yongxin Physical Review Letters, Vol. 113, Issue 3 https://doi.org/10.1103/PhysRevLett.113.036402	journal	July 2014
Antiferromagnetism and d -wave superconductivity in cuprates: A cluster dynamical mean-field theory Lichtenstein, A. I.; Katsnelson, M. I. Physical Review B, Vol. 62, Issue 14 https://doi.org/10.1103/PhysRevB.62.R9283	journal	October 2000
Bonding Trends Traversing the Tetravalent Actinide Series: Synthesis, Structural, and Computational Analysis of An ^IV ( ^Ar acnac) ₄ Complexes (An = Th, U, Np, Pu; ^Ar acnac = Ar N C(Ph)CHC(Ph) O ; Ar = 3,5- ^t Bu ₂ C ₆ H ₃ ) Schnaars, David D.; Gaunt, Andrew J.; Hayton, Trevor W. Inorganic Chemistry, Vol. 51, Issue 15 https://doi.org/10.1021/ic301109f	journal	July 2012
Synthesis, Structure, and Spectroscopic Properties of Am(IO ₃ ) ₃ and the Photoluminescence Behavior of Cm(IO ₃ ) ₃ Sykora, Richard E.; Assefa, Zerihun; Haire, Richard G. Inorganic Chemistry, Vol. 44, Issue 16 https://doi.org/10.1021/ic050386k	journal	August 2005
Structure validation in chemical crystallography Spek, Anthony L. Acta Crystallographica Section D Biological Crystallography, Vol. 65, Issue 2, p. 148-155 https://doi.org/10.1107/S090744490804362X	journal	January 2009
Directed evolution of the periodic table: probing the electronic structure of late actinides Marsh, M. L.; Albrecht-Schmitt, T. E. Dalton Transactions, Vol. 46, Issue 29 https://doi.org/10.1039/C7DT00664K	journal	January 2017
Evaluation of f-element borate chemistry Silver, Mark A.; Albrecht-Schmitt, Thomas E. Coordination Chemistry Reviews, Vol. 323 https://doi.org/10.1016/j.ccr.2016.02.015	journal	September 2016
Structural properties of plutonium from first-principles theory Söderlind, Per; Wills, J. M.; Johansson, B. Physical Review B, Vol. 55, Issue 4 https://doi.org/10.1103/PhysRevB.55.1997	journal	January 1997
Periodic Trends in Lanthanide and Actinide Phosphonates: Discontinuity between Plutonium and Americium Diwu, Juan; Grant, Daniel J.; Wang, Shuao Inorganic Chemistry, Vol. 51, Issue 12 https://doi.org/10.1021/ic300742p	journal	June 2012
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
Crystal growth and crystal structure of KTb(CrO4)2 Bueno, I.; Parada, C.; Hermoso, J. A. Journal of Solid State Chemistry, Vol. 85, Issue 1 https://doi.org/10.1016/S0022-4596(05)80063-5	journal	March 1990
Formation of a Eu( iii ) borate solid species from a weak Eu( iii ) borate complex in aqueous solution Schott, Juliane; Kretzschmar, Jerome; Acker, Margret Dalton Trans., Vol. 43, Issue 30 https://doi.org/10.1039/C4DT00843J	journal	January 2014
Toward reliable density functional methods without adjustable parameters: The PBE0 model Adamo, Carlo; Barone, Vincenzo The Journal of Chemical Physics, Vol. 110, Issue 13 https://doi.org/10.1063/1.478522	journal	April 1999
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
Incorporation of Technetium into Spinel Ferrites Lukens, Wayne W.; Magnani, Nicola; Tyliszczak, Tolek Environmental Science & Technology, Vol. 50, Issue 23 https://doi.org/10.1021/acs.est.6b04209	journal	November 2016
Demonstration of the LUCA process for the separation of americium(III) from curium(III), californium(III), and lanthanides(III) in acidic solution using a synergistic mixture of bis(chlorophenyl)dithiophosphinic acid and tris(2-ethylhexyl)phosphate Modolo, Giuseppe; Kluxen, Paul; Geist, Andreas Radiochimica Acta, Vol. 98, Issue 4 https://doi.org/10.1524/ract.2010.1708	journal	January 2010
Experimental and Theoretical Comparison of Actinide and Lanthanide Bonding in M[N(EPR ₂ ) ₂ ] ₃ Complexes (M = U, Pu, La, Ce; E = S, Se, Te; R = Ph, i Pr, H) Gaunt, Andrew J.; Reilly, Sean D.; Enriquez, Alejandro E. Inorganic Chemistry, Vol. 47, Issue 1 https://doi.org/10.1021/ic701618a	journal	January 2008
Transition metal iodates. II. Crystallographic, magnetic, and nonlinear optic survey of the 3d iodates Abrahams, S. C.; Sherwood, R. C.; Bernstein, J. L. Journal of Solid State Chemistry, Vol. 7, Issue 2 https://doi.org/10.1016/0022-4596(73)90155-2	journal	June 1973
Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf( ii ) Dau, Phuong D.; Shuh, David K.; Sturzbecher-Hoehne, Manuel Dalton Transactions, Vol. 45, Issue 31 https://doi.org/10.1039/C6DT02414A	journal	January 2016
Hydroxypyridinonate Complex Stability of Group (IV) Metals and Tetravalent f-Block Elements: The Key to the Next Generation of Chelating Agents for Radiopharmaceuticals Sturzbecher-Hoehne, Manuel; Choi, Taylor A.; Abergel, Rebecca J. Inorganic Chemistry, Vol. 54, Issue 7 https://doi.org/10.1021/acs.inorgchem.5b00033	journal	March 2015
Dynamical mean-field theory of strongly correlated fermion systems and the limit of infinite dimensions Georges, Antoine; Kotliar, Gabriel; Krauth, Werner Reviews of Modern Physics, Vol. 68, Issue 1 https://doi.org/10.1103/RevModPhys.68.13	journal	January 1996
New iodate materials as potential laser matrices. Preparation and characterisation of α-M(IO3)3 (M=Y, Dy) and β-M(IO3)3 (M=Y, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er). Structural evolution as a function of the Ln3+ cationic radius Phanon, Delphine; Mosset, Alain; Gautier-Luneau, Isabelle Solid State Sciences, Vol. 9, Issue 6 https://doi.org/10.1016/j.solidstatesciences.2007.04.004	journal	June 2007
Spontaneous Partitioning of Californium from Curium: Curious Cases from the Crystallization of Curium Coordination Complexes Cary, Samantha K.; Silver, Mark A.; Liu, Guokui Inorganic Chemistry, Vol. 54, Issue 23 https://doi.org/10.1021/acs.inorgchem.5b02052	journal	November 2015
Polyhedral Structures with an Odd Number of Vertices: Nine-Coordinate Metal Compounds Ruiz-Martínez, Antonio; Casanova, David; Alvarez, Santiago Chemistry - A European Journal, Vol. 14, Issue 4 https://doi.org/10.1002/chem.200701137	journal	January 2008
Generalized phase diagram for the rare-earth elements: Calculations and correlations of bulk properties Johansson, Börje; Rosengren, Anders Physical Review B, Vol. 11, Issue 8 https://doi.org/10.1103/PhysRevB.11.2836	journal	April 1975
Variational versus Perturbational Treatment of Spin–Orbit Coupling in Relativistic Density Functional Calculations of Electronic g Factors: Effects from Spin-Polarization and Exact Exchange Verma, Prakash; Autschbach, Jochen Journal of Chemical Theory and Computation, Vol. 9, Issue 2 https://doi.org/10.1021/ct3009864	journal	December 2012
Spectrum analysis of U 3+ :LaCl 3 Crosswhite, H. M.; Crosswhite, H.; Carnall, W. T. The Journal of Chemical Physics, Vol. 72, Issue 9 https://doi.org/10.1063/1.439742	journal	May 1980
A review of the demonstration of innovative solvent extraction processes for the recovery of trivalent minor actinides from PUREX raffinate Modolo, Giuseppe; Wilden, A.; Geist, Andreas Radiochimica Acta, Vol. 100, Issue 8-9 https://doi.org/10.1524/ract.2012.1962	journal	August 2012
Chelation and stabilization of berkelium in oxidation state +IV Deblonde, Gauthier J. -P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B. Nature Chemistry, Vol. 9, Issue 9 https://doi.org/10.1038/nchem.2759	journal	April 2017
High-Resolution Solid-State Oxygen-17 NMR of Actinide-Bearing Compounds: An Insight into the 5f Chemistry Martel, Laura; Magnani, Nicola; Vigier, Jean-Francois Inorganic Chemistry, Vol. 53, Issue 13 https://doi.org/10.1021/ic5007555	journal	June 2014
Comparison of Covalency in the Complexes of Trivalent Actinide and Lanthanide Cations Jensen, Mark P.; Bond, Andrew H. Journal of the American Chemical Society, Vol. 124, Issue 33 https://doi.org/10.1021/ja0178620	journal	August 2002
Using Phosphonates to Probe Structural Differences Between Transuranium Elements and Their Proposed Surrogates Diwu, Juan; Nelson, Anna-Gay D.; Albrecht-Schmitt, Thomas E. Comments on Inorganic Chemistry, Vol. 31, Issue 1-2 https://doi.org/10.1080/02603590903519988	journal	March 2010