The duality of electron localization and covalency in lanthanide and actinide metallocenes
Abstract
Previous magnetic, spectroscopic, and theoretical studies of cerocene, Ce(C8H8)2, have provided evidence for non-negligible 4f-electron density on Ce and implied that charge transfer from the ligands occurs as a result of covalent bonding. Strong correlations of the localized 4f-electrons to the delocalized ligand π-system result in emergence of Kondo-like behavior and other quantum chemical phenomena that are rarely observed in molecular systems. In this study, Ce(C8H8)2 is analyzed experimentally using carbon K-edge and cerium M5,4-edge X-ray absorption spectroscopies (XAS), and computationally using configuration interaction (CI) calculations and density functional theory (DFT) as well as time-dependent DFT (TDDFT). Both spectroscopic approaches provide strong evidence for ligand → metal electron transfer as a result of Ce 4f and 5d mixing with the occupied C 2p orbitals of the C8H82– ligands. Specifically, the Ce M5,4-edge XAS and CI calculations show that the contribution of the 4f1, or Ce3+, configuration to the ground state of Ce(C8H8)2 is similar to strongly correlated materials such as CeRh3 and significantly larger than observed for other formally Ce4+ compounds including CeO2 and CeCl62–. Pre-edge features in the experimental and TDDFT-simulated C K-edge XAS provide unequivocal evidence for C 2p and Ce 4f covalent orbital mixing in the δ-antibondingmore »
- Authors:
-
[2];
[3];
[2];
[1];
[1];
[4];
- Lawrence Berkeley National Laboratory; Berkeley; USA
- Los Alamos National Laboratory; Los Alamos; USA
- Colgate University; Hamilton; USA
- California State Polytechnic University; Pomona; USA
- Publication Date:
- 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). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
- OSTI Identifier:
- 1599477
- Alternate Identifier(s):
- OSTI ID: 1634954; OSTI ID: 1756326
- Report Number(s):
- LA-UR-19-24200
Journal ID: ISSN 2041-6520; CSHCBM
- Grant/Contract Number:
- 89233218CNA000001; AC02-05CH11231; AC52-06NA25396; CHE160059
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 10; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Smiles, Danil E., Batista, Enrique R., Booth, Corwin H., Clark, David L., Keith, Jason M., Kozimor, Stosh A., Martin, Richard L., Minasian, Stefan G., Shuh, David K., Stieber, S. Chantal E., and Tyliszczak, Tolek. The duality of electron localization and covalency in lanthanide and actinide metallocenes. United Kingdom: N. p., 2020.
Web. doi:10.1039/C9SC06114B.
Smiles, Danil E., Batista, Enrique R., Booth, Corwin H., Clark, David L., Keith, Jason M., Kozimor, Stosh A., Martin, Richard L., Minasian, Stefan G., Shuh, David K., Stieber, S. Chantal E., & Tyliszczak, Tolek. The duality of electron localization and covalency in lanthanide and actinide metallocenes. United Kingdom. doi:10.1039/C9SC06114B.
Smiles, Danil E., Batista, Enrique R., Booth, Corwin H., Clark, David L., Keith, Jason M., Kozimor, Stosh A., Martin, Richard L., Minasian, Stefan G., Shuh, David K., Stieber, S. Chantal E., and Tyliszczak, Tolek. Wed .
"The duality of electron localization and covalency in lanthanide and actinide metallocenes". United Kingdom. doi:10.1039/C9SC06114B.
@article{osti_1599477,
title = {The duality of electron localization and covalency in lanthanide and actinide metallocenes},
author = {Smiles, Danil E. and Batista, Enrique R. and Booth, Corwin H. and Clark, David L. and Keith, Jason M. and Kozimor, Stosh A. and Martin, Richard L. and Minasian, Stefan G. and Shuh, David K. and Stieber, S. Chantal E. and Tyliszczak, Tolek},
abstractNote = {Previous magnetic, spectroscopic, and theoretical studies of cerocene, Ce(C8H8)2, have provided evidence for non-negligible 4f-electron density on Ce and implied that charge transfer from the ligands occurs as a result of covalent bonding. Strong correlations of the localized 4f-electrons to the delocalized ligand π-system result in emergence of Kondo-like behavior and other quantum chemical phenomena that are rarely observed in molecular systems. In this study, Ce(C8H8)2 is analyzed experimentally using carbon K-edge and cerium M5,4-edge X-ray absorption spectroscopies (XAS), and computationally using configuration interaction (CI) calculations and density functional theory (DFT) as well as time-dependent DFT (TDDFT). Both spectroscopic approaches provide strong evidence for ligand → metal electron transfer as a result of Ce 4f and 5d mixing with the occupied C 2p orbitals of the C8H82– ligands. Specifically, the Ce M5,4-edge XAS and CI calculations show that the contribution of the 4f1, or Ce3+, configuration to the ground state of Ce(C8H8)2 is similar to strongly correlated materials such as CeRh3 and significantly larger than observed for other formally Ce4+ compounds including CeO2 and CeCl62–. Pre-edge features in the experimental and TDDFT-simulated C K-edge XAS provide unequivocal evidence for C 2p and Ce 4f covalent orbital mixing in the δ-antibonding orbitals of e2u symmetry, which are the unoccupied counterparts to the occupied, ligand-based δ-bonding e2u orbitals. The C K-edge peak intensities, which can be compared directly to the C 2p and Ce 4f orbital mixing coefficients determined by DFT, show that covalency in Ce(C8H8)2 is comparable in magnitude to values reported previously for U(C8H8)2. An intuitive model is presented to show how similar covalent contributions to the ground state can have different impacts on the overall stability of f-element metallocenes.},
doi = {10.1039/C9SC06114B},
journal = {Chemical Science},
number = 10,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {1}
}
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C9SC06114B
DOI: 10.1039/C9SC06114B
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 4 works
Citation information provided by
Web of Science
Web of Science
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:
Covalency in AnCp4 (An = Th–Cm): a comparison of molecular orbital, natural population and atoms-in-molecules analyses
journal, January 2010
- Tassell, Matthew J.; Kaltsoyannis, Nikolas
- Dalton Transactions, Vol. 39, Issue 29
Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment
journal, January 2017
- Fieser, Megan E.; Palumbo, Chad T.; La Pierre, Henry S.
- Chem. Sci., Vol. 8, Issue 11
A Theoretical Study on Divalent Heavier Group 14 Complexes as Promising Donor Ligands for Building Uranium–Metal Bonds
journal, April 2019
- Chi, Xiao-Wang; Wu, Qun-Yan; Lan, Jian-Hui
- Organometallics, Vol. 38, Issue 9
Bond Covalency and Oxidation State of Actinide Ions Complexed with Therapeutic Chelating Agent 3,4,3-LI(1,2-HOPO)
journal, April 2018
- Kelley, Morgan P.; Deblonde, Gauthier J. -P.; Su, Jing
- Inorganic Chemistry, Vol. 57, Issue 9
Ab initio pseudopotentials for Hg through Rn : I. Parameter sets and atomic calculations
journal, December 1991
- Küchle, W.; Dolg, M.; Stoll, H.
- Molecular Physics, Vol. 74, Issue 6
Application of the Hubbard Model to Cp* 2 Yb(bipy), a Model System for Strong Exchange Coupling in Lanthanide Systems
journal, September 2012
- Lukens, Wayne W.; Magnani, Nicola; Booth, Corwin H.
- Inorganic Chemistry, Vol. 51, Issue 19
Photoelectron spectroscopy of Ce(η-C5H5)3 – Accessing two ion states on 4f ionization
journal, December 2006
- Coreno, Marcello; de Simone, Monica; Green, Jennifer C.
- Chemical Physics Letters, Vol. 432, Issue 1-3
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
journal, March 2012
- Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.
- Journal of the American Chemical Society, Vol. 134, Issue 12
Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M–S bonding for MS 4 2− (M = Cr, Mo, W) dianions
journal, January 2014
- Olson, Angela C.; Keith, Jason M.; Batista, Enrique R.
- Dalton Trans., Vol. 43, Issue 46
Zur Elektronenstruktur metallorganischer Komplexe der f-Elemente LXI. Welche Oxidationszahl hat Cer im tiefvioletten 1,1′,4,4′-Tetrakis(trimethylsilyl)cerocen?
journal, April 2005
- Amberger, Hanns-Dieter; Reddmann, Hauke; Edelmann, Frank T.
- Journal of Organometallic Chemistry, Vol. 690, Issue 9
Quantitative Evidence for Lanthanide-Oxygen Orbital Mixing in CeO 2 , PrO 2 , and TbO 2
journal, November 2017
- Minasian, Stefan G.; Batista, Enrique R.; Booth, Corwin H.
- Journal of the American Chemical Society, Vol. 139, Issue 49
Uncovering f-element bonding differences and electronic structure in a series of 1 : 3 and 1 : 4 complexes with a diselenophosphinate ligand
journal, January 2013
- Jones, Matthew B.; Gaunt, Andrew J.; Gordon, John C.
- Chemical Science, Vol. 4, Issue 3
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 )
journal, January 2011
- Kirker, Ian; Kaltsoyannis, Nikolas
- Dalton Trans., Vol. 40, Issue 1
An Alkali Metal-Capped Cerium(IV) Imido Complex
journal, May 2016
- Solola, Lukman A.; Zabula, Alexander V.; Dorfner, Walter L.
- Journal of the American Chemical Society, Vol. 138, Issue 22
Covalency Trends in Group IV Metallocene Dichlorides. Chlorine K-Edge X-Ray Absorption Spectroscopy and Time Dependent-Density Functional Theory
journal, June 2008
- Kozimor, Stosh A.; Yang, Ping; Batista, Enrique R.
- Inorganic Chemistry, Vol. 47, Issue 12
Covalency in Metal–Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory
journal, January 2013
- Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.
- Journal of the American Chemical Society, Vol. 135, Issue 5
Energy‐adjusted pseudopotentials for the actinides. Parameter sets and test calculations for thorium and thorium monoxide
journal, May 1994
- Küchle, W.; Dolg, M.; Stoll, H.
- The Journal of Chemical Physics, Vol. 100, Issue 10
A Macrocyclic Chelator That Selectively Binds Ln 4+ over Ln 3+ by a Factor of 10 29
journal, June 2016
- Pham, Tiffany A.; Altman, Alison B.; Stieber, S. Chantal E.
- Inorganic Chemistry, Vol. 55, Issue 20
M ‐edge x‐ray absorption spectroscopy of 4 f instabilities in rare‐earth systems (invited)
journal, March 1984
- Kaindl, G.; Kalkowski, G.; Brewer, W. D.
- Journal of Applied Physics, Vol. 55, Issue 6
Emergence of comparable covalency in isostructural cerium( iv )– and uranium( iv )–carbon multiple bonds
journal, January 2016
- Gregson, Matthew; Lu, Erli; Tuna, Floriana
- Chemical Science, Vol. 7, Issue 5
Elucidating bonding preferences in tetrakis(imido)uranate(VI) dianions
journal, April 2017
- Anderson, Nickolas H.; Xie, Jing; Ray, Debmalya
- Nature Chemistry, Vol. 9, Issue 9
Pyrazolates advance cerium chemistry: a Ce III /Ce IV redox equilibrium with benzoquinone
journal, January 2017
- Werner, Daniel; Deacon, Glen B.; Junk, Peter C.
- Dalton Transactions, Vol. 46, Issue 19
Is Cerocene Really a Ce(III) Compound? All-Electron Spin−Orbit Coupled CASPT2 Calculations on M(η 8 -C 8 H 8 ) 2 (M = Th, Pa, Ce)
journal, March 2009
- Kerridge, Andrew; Coates, Rosemary; Kaltsoyannis, Nikolas
- The Journal of Physical Chemistry A, Vol. 113, Issue 12
Covalency in f-element complexes
journal, January 2013
- Neidig, Michael L.; Clark, David L.; Martin, Richard L.
- Coordination Chemistry Reviews, Vol. 257, Issue 2
Bis(permethylpentalene)cerium ? another ambiguity in lanthanide oxidation state
journal, January 2007
- Ashley, Andrew; Balazs, Gabor; Cowley, Andrew
- Chemical Communications, Issue 15
3d x-ray-absorption lines and the 3 4 multiplets of the lanthanides
journal, October 1985
- Thole, B. T.; van der Laan, G.; Fuggle, J. C.
- Physical Review B, Vol. 32, Issue 8
Magnetic circular dichroism of UCl 6 − in the ligand-to-metal charge-transfer spectral region
journal, January 2017
- Gendron, Frédéric; Fleischauer, Valerie E.; Duignan, Thomas J.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 26
Towards understanding of lanthanide–transition metal bonding: investigations of the first Ce–Fe bonded complex
journal, January 2018
- Burns, Corey P.; Yang, Xin; Sung, Siyoung
- Chemical Communications, Vol. 54, Issue 77
Cerocene Revisited: The Electronic Structure of and Interconversion Between Ce 2 (C 8 H 8 ) 3 and Ce(C 8 H 8 ) 2
journal, February 2009
- Walter, Marc D.; Booth, Corwin H.; Lukens, Wayne W.
- Organometallics, Vol. 28, Issue 3
Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning
journal, June 2012
- Kaltsoyannis, Nikolas
- Inorganic Chemistry, Vol. 52, Issue 7
Self-Contained Kondo Effect in Single Molecules
journal, December 2005
- Booth, C. H.; Walter, M. D.; Daniel, M.
- Physical Review Letters, Vol. 95, Issue 26
A Pseudotetrahedral Uranium(V) Complex
journal, June 2018
- Tondreau, Aaron M.; Duignan, Thomas J.; Stein, Benjamin W.
- Inorganic Chemistry, Vol. 57, Issue 14
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, January 2018
- Galley, Shane S.; Arico, Alexandra A.; Lee, Tsung-Han
- Journal of the American Chemical Society, Vol. 140, Issue 5
Low-lying electronic states of lanthanocenes and actinocenes M(C8H8)2 (M=Nd, Tb, Yb, U)
journal, September 1997
- Liu, Wenjian; Dolg, Michael; Fulde, Peter
- The Journal of Chemical Physics, Vol. 107, Issue 9
resonant photoemission spectra at the Ce edge of
journal, September 2000
- Ogasawara, H.; Kotani, A.; Le Fèvre, P.
- Physical Review B, Vol. 62, Issue 12
New 7r-cyclooctate'I'raenyl and iT-cyclopentadienyl complexes of cerium
journal, July 1976
- Greco, Alberto; Cesca, Sebastiano; Bertolini, Wiglielmo
- Journal of Organometallic Chemistry, Vol. 113, Issue 4
A method for normalization of X-ray absorption spectra
journal, June 2005
- Weng, Tsu-Chien; Waldo, Geoffrey S.; Penner-Hahn, James E.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
f-Orbital covalency in the actinocenes (An = Th–Cm): multiconfigurational studies and topological analysis
journal, January 2014
- Kerridge, Andrew
- RSC Adv., Vol. 4, Issue 24
Electron Localization in the Ground State of the Ruthenium Blue Dimer
journal, June 2007
- Batista, Enrique R.; Martin, Richard L.
- Journal of the American Chemical Society, Vol. 129, Issue 23
Variable Photon Energy Photoelectron Spectroscopy and Magnetism of YbCp 3 and LuCp 3 †
journal, November 2010
- Coreno, Marcello; de Simone, Monica; Coates, Rosemary
- Organometallics, Vol. 29, Issue 21
Coulomb blockade and the Kondo effect in single-atom transistors
journal, June 2002
- Park, Jiwoong; Pasupathy, Abhay N.; Goldsmith, Jonas I.
- Nature, Vol. 417, Issue 6890
Kondo resonance in a single-molecule transistor
journal, June 2002
- Liang, Wenjie; Shores, Matthew P.; Bockrath, Marc
- Nature, Vol. 417, Issue 6890
Uranium–Ligand Multiple Bonding in Uranyl Analogues, [L═U═L] n + , and the Inverse Trans Influence
journal, December 2012
- La Pierre, Henry S.; Meyer, Karsten
- Inorganic Chemistry, Vol. 52, Issue 2
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988
- Lee, Chengteh; Yang, Weitao; Parr, Robert G.
- Physical Review B, Vol. 37, Issue 2
A computational investigation of orbital overlap versus energy degeneracy covalency in [UE 2 ] 2+ (E = O, S, Se, Te) complexes
journal, January 2020
- Platts, James A.; Baker, Robert J.
- Dalton Transactions, Vol. 49, Issue 4
Covalency in the 4f Shell of tris -Cyclopentadienyl Ytterbium (YbCp 3 )—A Spectroscopic Evaluation
journal, December 2011
- Denning, Robert G.; Harmer, Jeffrey; Green, Jennifer C.
- Journal of the American Chemical Society, Vol. 133, Issue 50
Sulfur K-edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory of Dithiophosphinate Extractants: Minor Actinide Selectivity and Electronic Structure Correlations
journal, August 2012
- Daly, Scott R.; Keith, Jason M.; Batista, Enrique R.
- Journal of the American Chemical Society, Vol. 134, Issue 35
Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex
journal, July 2019
- Rice, Natalie T.; Popov, Ivan A.; Russo, Dominic R.
- Journal of the American Chemical Society, Vol. 141, Issue 33
Uranium Tetrakis-Aryloxide Derivatives Supported by Tetraazacyclododecane: Synthesis of Air-Stable, Coordinatively-Unsaturated U(IV) and U(V) Complexes
journal, November 2016
- Hümmer, Julian; Heinemann, Frank W.; Meyer, Karsten
- Inorganic Chemistry, Vol. 56, Issue 6
Ion pair complex formed between bis(cyclooctatetraenyl)cerium(III) anion and an ether-coordinated potassium cation. Crystal and molecular structure of [K(CH3OCH2CH2)2O][Ce(C8H8)2]
journal, December 1972
- Hodgson, Keith O.; Raymond, Kenneth N.
- Inorganic Chemistry, Vol. 11, Issue 12
The Oxidation State of Ce in the Sandwich Molecule Cerocene
journal, January 1996
- Edelstein, N. M.; Allen, P. G.; Bucher, J. J.
- Journal of the American Chemical Society, Vol. 118, Issue 51
Fine-tuning the Local Symmetry to Attain Record Blocking Temperature and Magnetic Remanence in a Single-Ion Magnet
journal, March 2014
- Ungur, Liviu; Le Roy, Jennifer J.; Korobkov, Ilia
- Angewandte Chemie International Edition, Vol. 53, Issue 17
The CTM4XAS program for EELS and XAS spectral shape analysis of transition metal L edges
journal, October 2010
- Stavitski, Eli; de Groot, Frank M. F.
- Micron, Vol. 41, Issue 7
Single but Stronger UO, Double but Weaker UNMe Bonds: The Tale Told by Cp 2 UO and Cp 2 UNR
journal, September 2007
- Barros, Noémi; Maynau, Daniel; Maron, Laurent
- Organometallics, Vol. 26, Issue 20
Optimization of analysis of soft X-ray spectromicroscopy at the Ca 2p edge
journal, June 2009
- Hanhan, S.; Smith, A. M.; Obst, M.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 173, Issue 1
Intermediate-Valence Tautomerism in Decamethylytterbocene Complexes of Methyl-Substituted Bipyridines
journal, December 2010
- Booth, Corwin H.; Kazhdan, Daniel; Werkema, Evan L.
- Journal of the American Chemical Society, Vol. 132, Issue 49
Formally tetravalent cerium and thorium compounds: a configuration interaction study of cerocene Ce(C8H8)2 and thorocene Th(C8H8)2 using energy-adjusted quasirelativistic ab initio pseudopotentials
journal, June 1995
- Dolg, M.; Fulde, P.; Stoll, H.
- Chemical Physics, Vol. 195, Issue 1-3
Comparison of non-relativistic and quasi-relativistic SCF-Xα scattered-wave calculations of uranocene, thorocene and cerocene
journal, June 1984
- Rösch, N.
- Inorganica Chimica Acta, Vol. 94, Issue 6
Influence of the Torsion Angle in 3,3′-Dimethyl-2,2′-bipyridine on the Intermediate Valence of Yb in (C 5 Me 5 ) 2 Yb(3,3′-Me 2 -bipy)
journal, September 2013
- Nocton, Grégory; Booth, Corwin H.; Maron, Laurent
- Organometallics, Vol. 32, Issue 19
Covalency in bis([8]annulene)uranium from photoelectron spectroscopy with variable photon energy
journal, March 1989
- Brennan, John G.; Green, Jennifer C.; Redfern, Catherine M.
- Journal of the American Chemical Society, Vol. 111, Issue 7
Magnetic Properties of a Terbium-[1]Ferrocenophane Complex: Analogies between Lanthanide-Ferrocenophane and Lanthanide-Bis-phthalocyanine Complexes
journal, June 2018
- Latendresse, Trevor P.; Vieru, Veacheslav; Wilkins, Branford O.
- Angewandte Chemie International Edition, Vol. 57, Issue 27
A relativistic lcao hartree-fock-slater investigation of the electronic structure of the actinocenes M(COT)2, M = Th, Pa, U, Np AND Pu
journal, June 1988
- Boerrigter, P. M.; Baerends, E. J.; Snijders, J. G.
- Chemical Physics, Vol. 122, Issue 3
Comparative studies of quasi-relativistic density functional methods for the description of lanthanide and actinide complexes
journal, May 2003
- Vetere, Valentina; Maldivi, Pascale; Adamo, Carlo
- Journal of Computational Chemistry, Vol. 24, Issue 7
Lanthanide Photocatalysis
journal, October 2018
- Qiao, Yusen; Schelter, Eric J.
- Accounts of Chemical Research, Vol. 51, Issue 11
Segmented contraction scheme for small-core actinide pseudopotential basis sets
journal, March 2004
- Cao, Xiaoyan; Dolg, Michael
- Journal of Molecular Structure: THEOCHEM, Vol. 673, Issue 1-3
Theory of core-level spectroscopy of rare-earth oxides
journal, December 1992
- Kotani, Akio; Ogasawara, Haruhiko
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 60, Issue 4
Wasserstoff-Verschiebungen, II. Über das thermische Gleichgewicht zwischen Cyclooctatrien-(1.3.6) und Cyclooctatrien-(1.3.5)
journal, February 1964
- Roth, Wolfgang R.
- Justus Liebigs Annalen der Chemie, Vol. 671, Issue 1
Ground state calculations of di‐π‐cyclooctatetraene cerium
journal, February 1991
- Dolg, Michael; Fulde, Peter; Küchle, Wolfgang
- The Journal of Chemical Physics, Vol. 94, Issue 4
Covalency in CeIV and UIV Halide and N-Heterocyclic Carbene Bonds
journal, July 2010
- Arnold, Polly L.; Turner, Zoë R.; Kaltsoyannis, Nikolas
- Chemistry - A European Journal, Vol. 16, Issue 31
Orbital localization and delocalization effects in the U configuration: Impurity problem
journal, May 1998
- Koga, Mikito; Liu, Wenjian; Dolg, Michael
- Physical Review B, Vol. 57, Issue 17
4f occupation and hybridization from M-shell excitations in Rare-Earth materials
journal, February 1985
- Kaindl, G.; Kalkowski, G.; Brewer, W. D.
- Journal of Magnetism and Magnetic Materials, Vol. 47-48
Covalency in f-element bonds
journal, October 2002
- Choppin, Gregory R.
- Journal of Alloys and Compounds, Vol. 344, Issue 1-2
Spectator and participator processes in the resonant photon-in and photon-out spectra at the Ce L3 edge of CeO2
journal, July 2012
- Kotani, A.; Kvashnina, K. O.; Butorin, S. M.
- The European Physical Journal B, Vol. 85, Issue 8
Multiplet effects in X-ray spectroscopy
journal, January 2005
- Groot, Frank de
- Coordination Chemistry Reviews, Vol. 249, Issue 1-2
Ground States, Excited States, and Metal−Ligand Bonding in Rare Earth Hexachloro Complexes: A DFT-Based Ligand Field Study
journal, April 2005
- Atanasov, M.; Daul, C.; Güdel, H. U.
- Inorganic Chemistry, Vol. 44, Issue 8
L 3 and M 4,5 absorption edges of intermediate valent cerium unravelled by resonant photoemission and resonant Auger spectroscopy
journal, May 1999
- Le Fèvre, P.; Magnan, H.; Vogel, J.
- Journal of Synchrotron Radiation, Vol. 6, Issue 3
Resonant inelastic x-ray scattering at the Ce edge of and : Implications for the valence of and related phenomena
journal, July 2005
- Sham, T. K.; Gordon, R. A.; Heald, S. M.
- Physical Review B, Vol. 72, Issue 3
Probing the Reactivity of the Ce═O Multiple Bond in a Cerium(IV) Oxo Complex
journal, May 2016
- So, Yat-Ming; Li, Yang; Au-Yeung, Ka-Chun
- Inorganic Chemistry, Vol. 55, Issue 20
Pursuit of Record Breaking Energy Barriers: A Study of Magnetic Axiality in Diamide Ligated Dy III Single-Molecule Magnets
journal, January 2017
- Harriman, Katie L. M.; Brosmer, Jonathan L.; Ungur, Liviu
- Journal of the American Chemical Society, Vol. 139, Issue 4
Oxidation state and covalency in f-element metallocenes (M = Ce, Th, Pu): a combined CASSCF and topological study
journal, January 2013
- Kerridge, Andrew
- Dalton Transactions, Vol. 42, Issue 46
Investigations of the Electronic Structure of Arene-Bridged Diuranium Complexes
journal, January 2013
- Vlaisavljevich, Bess; Diaconescu, Paula L.; Lukens, Wayne L.
- Organometallics, Vol. 32, Issue 5
Structural criteria for the mode of bonding of organoactinides and -lanthanides and related compounds
journal, August 1980
- Raymond, Kenneth N.; Eigenbrot, Charles W.
- Accounts of Chemical Research, Vol. 13, Issue 8
Synthesis and Characterization of Tris-chelate Complexes for Understanding f -Orbital Bonding in Later Actinides
journal, January 2019
- Galley, Shane S.; Pattenaude, Scott A.; Gaggioli, Carlo Alberto
- Journal of the American Chemical Society, Vol. 141, Issue 6
On the Upper Limits of Oxidation States in Chemistry
journal, February 2018
- Hu, Shu-Xian; Li, Wan-Lu; Lu, Jun-Bo
- Angewandte Chemie International Edition, Vol. 57, Issue 12
Effective core potential methods for the lanthanides
journal, April 1993
- Cundari, Thomas R.; Stevens, Walter J.
- The Journal of Chemical Physics, Vol. 98, Issue 7
An investigation of the electronic structure of bis(η-cyclo-octatetraene)-actinoids by helium-( I ) and -( II ) photoelectron spetroscopy
journal, January 1977
- Clark, John P.; Green, Jennifer C.
- J. Chem. Soc., Dalton Trans., Issue 5
Quantifying the σ and π Interactions between U(V) f Orbitals and Halide, Alkyl, Alkoxide, Amide and Ketimide Ligands
journal, July 2013
- Lukens, Wayne W.; Edelstein, Norman M.; Magnani, Nicola
- Journal of the American Chemical Society, Vol. 135, Issue 29
Metal and Ligand K-Edge XAS of Organotitanium Complexes: Metal 4p and 3d Contributions to Pre-edge Intensity and Their Contributions to Bonding
journal, January 2005
- DeBeer George, Serena; Brant, Patrick; Solomon, Edward I.
- Journal of the American Chemical Society, Vol. 127, Issue 2
Reversible Sigma C–C Bond Formation Between Phenanthroline Ligands Activated by (C 5 Me 5 ) 2 Yb
journal, June 2014
- Nocton, Grégory; Lukens, Wayne W.; Booth, Corwin H.
- Journal of the American Chemical Society, Vol. 136, Issue 24
Electronic structure of nanoporous ceria from x-ray absorption spectroscopy and atomic multiplet calculations
journal, December 2007
- Kucheyev, S. O.; Clapsaddle, B. J.; Wang, Y. M.
- Physical Review B, Vol. 76, Issue 23
Electronic structure and spectra of uranocene
journal, March 1989
- Chang, Agnes H. H.; Pitzer, Russell M.
- Journal of the American Chemical Society, Vol. 111, Issue 7
Ligand K-Edge X-ray Absorption Spectroscopy as a Probe of Ligand-Metal Bonding: Charge Donation and Covalency in Copper-Chloride Systems
journal, September 1994
- Shadle, Susan E.; Hedman, Britt; Hodgson, Keith O.
- Inorganic Chemistry, Vol. 33, Issue 19
Narrowing Due to Valence Mixing in the 3d Core Level Spectra for Ce Compounds
journal, July 1988
- Jo, Takeo; Kotani, Akio
- Journal of the Physical Society of Japan, Vol. 57, Issue 7
Decamethylytterbocene Complexes of Bipyridines and Diazabutadienes: Multiconfigurational Ground States and Open-Shell Singlet Formation
journal, May 2009
- Booth, Corwin H.; Walter, Marc D.; Kazhdan, Daniel
- Journal of the American Chemical Society, Vol. 131, Issue 18
Modeling the electronic states and magnetic properties derived from the f 1 configuration in lanthanocene and actinocene compounds
journal, January 2017
- Solis-Céspedes, Eduardo; Páez-Hernández, Dayán
- Dalton Transactions, Vol. 46, Issue 14
Cerium(IV) Imido Complexes: Structural, Computational, and Reactivity Studies
journal, February 2017
- Solola, Lukman A.; Zabula, Alexander V.; Dorfner, Walter L.
- Journal of the American Chemical Society, Vol. 139, Issue 6
Covalency in Lanthanides. An X-ray Absorption Spectroscopy and Density Functional Theory Study of LnCl 6 x – ( x = 3, 2)
journal, February 2015
- Löble, Matthias W.; Keith, Jason M.; Altman, Alison B.
- Journal of the American Chemical Society, Vol. 137, Issue 7
Pressure-induced changes in x-ray-absorption near-edge structure of Ce and Ce : Relevance to -electronic structure
journal, November 1988
- Kaindl, G.; Schmiester, G.; Sampathkumaran, E. V.
- Physical Review B, Vol. 38, Issue 14
Relativistic Density Functional Study of the Geometry, Electronic Transitions, Ionization Energies, and Vibrational Frequencies of Protactinocene, Pa(η 8 -C 8 H 8 ) 2
journal, November 1998
- Li, Jun; Bursten, Bruce E.
- Journal of the American Chemical Society, Vol. 120, Issue 44
Flipping the Oxidation State Formalism: Charge Distribution in Organometallic Complexes As Reported by Carbon Monoxide
journal, January 2017
- Wolczanski, Peter T.
- Organometallics, Vol. 36, Issue 3
Covalency in the actinide dioxides: Systematic study of the electronic properties using screened hybrid density functional theory
journal, July 2007
- Prodan, Ionut D.; Scuseria, Gustavo E.; Martin, Richard L.
- Physical Review B, Vol. 76, Issue 3
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 )
journal, July 2012
- Schnaars, David D.; Gaunt, Andrew J.; Hayton, Trevor W.
- Inorganic Chemistry, Vol. 51, Issue 15
Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
- Becke, Axel D.
- The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
CORE-HOLE EFFECT IN THE Ce L 3 X-RAY ABSORPTION SPECTRA OF CeO 2 AND CeFe 2 : NEW EXAMINATION BY USING RESONANT X-RAY EMISSION SPECTROSCOPY
journal, June 2013
- Kotani, A.
- Modern Physics Letters B, Vol. 27, Issue 16
Pentavalent Curium, Berkelium, and Californium in Nitrate Complexes: Extending Actinide Chemistry and Oxidation States
journal, July 2018
- Kovács, Attila; Dau, Phuong D.; Marçalo, Joaquim
- Inorganic Chemistry, Vol. 57, Issue 15
High resolution mapping of surface reduction in ceria nanoparticles
journal, January 2011
- Turner, Stuart; Lazar, Sorin; Freitag, Bert
- Nanoscale, Vol. 3, Issue 8
Ligand K-edge x-ray absorption spectroscopic studies: metal-ligand covalency in a series of transition metal tetrachlorides
journal, March 1995
- Shadle, Susan E.; Hedman, Britt; Hodgson, Keith O.
- Journal of the American Chemical Society, Vol. 117, Issue 8
Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple-Decker Arene-Bridged Cerium(II) Sandwich
journal, November 2017
- Kelly, Rory P.; Maron, Laurent; Scopelliti, Rosario
- Angewandte Chemie International Edition, Vol. 56, Issue 49
Tetravalent cerium carbene complexes
journal, January 2007
- Casely, Ian J.; Liddle, Stephen T.; Blake, Alexander J.
- Chemical Communications, Issue 47
Chelate-Free Synthesis of the U(II) Complex, [(C 5 H 3 (SiMe 3 ) 2 ) 3 U] 1– , Using Li and Cs Reductants and Comparative Studies of La(II) and Ce(II) Analogs
journal, August 2018
- Huh, Daniel N.; Ziller, Joseph W.; Evans, William J.
- Inorganic Chemistry, Vol. 57, Issue 18
Unprecedented Bending and Rearrangement of f-Element Sandwich Complexes Induced by Superbulky Cyclooctatetraenide Ligands
journal, February 2011
- Lorenz, Volker; Schmiege, Benjamin M.; Hrib, Cristian G.
- Journal of the American Chemical Society, Vol. 133, Issue 5
Molecular Complex of Tb in the +4 Oxidation State
journal, June 2019
- Palumbo, Chad T.; Zivkovic, Ivica; Scopelliti, Rosario
- Journal of the American Chemical Society, Vol. 141, Issue 25
Are the Ground States of the Later Actinocenes Multiconfigurational? All-Electron Spin−Orbit Coupled CASPT2 Calculations on An(η 8 -C 8 H 8 ) 2 (An = Th, U, Pu, Cm)
journal, July 2009
- Kerridge, Andrew; Kaltsoyannis, Nikolas
- The Journal of Physical Chemistry A, Vol. 113, Issue 30
Lanthanide(III) complexes with cyclooctatetraene dianion. Synthetic chemistry, characterization, and physical properties
journal, December 1973
- Hodgson, K. O.; Mares, F.; Starks, D. F.
- Journal of the American Chemical Society, Vol. 95, Issue 26
Two interpretations of the cerocene electronic ground state
journal, February 2014
- Mooßen, Oliver; Dolg, Michael
- Chemical Physics Letters, Vol. 594
Exchange coupling and magnetic blocking in dilanthanide complexes bridged by the multi-electron redox-active ligand 2,3,5,6-tetra(2-pyridyl)pyrazine
journal, January 2014
- Demir, Selvan; Nippe, Michael; Gonzalez, Miguel I.
- Chem. Sci., Vol. 5, Issue 12
Charge control of the inverse trans-influence
journal, January 2015
- La Pierre, Henry S.; Rosenzweig, Michael; Kosog, Boris
- Chemical Communications, Vol. 51, Issue 93
The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory
journal, January 2016
- Dumas, Thomas; Guillaumont, Dominique; Fillaux, Clara
- Physical Chemistry Chemical Physics, Vol. 18, Issue 4
Cerium(III) and Cerium(IV) Bis(η 8 -pentalene) Sandwich Complexes: Synthetic, Structural, Spectroscopic, and Theoretical Studies
journal, June 2007
- Balazs, Gabor; Cloke, F. Geoffrey N.; Green, Jennifer C.
- Organometallics, Vol. 26, Issue 13
New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory
journal, January 2014
- Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.
- Chem. Sci., Vol. 5, Issue 1
Emergence of the structure-directing role of f-orbital overlap-driven covalency
journal, February 2019
- Lu, Erli; Sajjad, Saira; Berryman, Victoria E. J.
- Nature Communications, Vol. 10, Issue 1
Structures of organo-f-element compounds differing in the oxidation state of the central metal: crystal structures of bis([8]annulene) complexes of cerium(IV), ytterbium(III), and uranium(III)
journal, June 1991
- Boussie, Thomas R.; Eisenberg, David C.; Rigsbee, John.
- Organometallics, Vol. 10, Issue 6
Bis(cyclooctatetraenyl)uranium (uranocene). A new class of sandwich complexes that utilize atomic f orbitals
journal, December 1968
- Streitwieser, Andrew.; Mueller-Westerhoff, Ulrich.
- Journal of the American Chemical Society, Vol. 90, Issue 26
Photoelectron spectra and bonding in cerocene, bis(.pi.-[8]annulene)cerium(IV)
journal, December 1985
- Streitwieser, Andrew; Kinsley, Steven A.; Rigsbee, John T.
- Journal of the American Chemical Society, Vol. 107, Issue 25
Carbon K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory Examination of Metal–Carbon Bonding in Metallocene Dichlorides
journal, September 2013
- Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.
- Journal of the American Chemical Society, Vol. 135, Issue 39
The electronic structure of actinide-containing molecules: a challenge to applied quantum chemistry
journal, July 1991
- Pepper, Melanie.; Bursten, Bruce E.
- Chemical Reviews, Vol. 91, Issue 5
A complete basis set model chemistry. II. Open‐shell systems and the total energies of the first‐row atoms
journal, May 1991
- Petersson, G. A.; Al‐Laham, Mohammad A.
- The Journal of Chemical Physics, Vol. 94, Issue 9
Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds
journal, January 2005
- Solomon, Edward I.; Hedman, Britt; Hodgson, Keith O.
- Coordination Chemistry Reviews, Vol. 249, Issue 1-2
The study of actinide chemistry with multiconfigurational quantum chemical methods
journal, January 2011
- Gagliardi, Laura
- International Journal of Quantum Chemistry, Vol. 111, Issue 13
Evidence for 5d-σ and 5d-π covalency in lanthanide sesquioxides from oxygen K-edge X-ray absorption spectroscopy
journal, January 2016
- Altman, Alison B.; Pacold, Joseph I.; Wang, Jian
- Dalton Transactions, Vol. 45, Issue 24
A Relativistic Study of the Electronic and Magnetic Properties of Cerocene and Thorocene and Its Anions
journal, April 2012
- Ferraro, Franklin; Barboza, Cristina Aparecida; Arratia-Pérez, Ramiro
- The Journal of Physical Chemistry A, Vol. 116, Issue 16
Heavy fermion semiconductors
journal, May 2000
- Riseborough, Peter S.
- Advances in Physics, Vol. 49, Issue 3
A proper account of core-polarization with pseudopotentials: single valence-electron alkali compounds
journal, July 1982
- Fuentealba, Patricio; Preuss, Heinzwerner; Stoll, Hermann
- Chemical Physics Letters, Vol. 89, Issue 5
Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides
journal, April 2016
- Zhang, Qingnan; Hu, Shu-Xian; Qu, Hui
- Angewandte Chemie International Edition, Vol. 55, Issue 24
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
Soft X-ray microscopy and spectroscopy at the molecular environmental science beamline at the Advanced Light Source
journal, February 2006
- Bluhm, H.; Andersson, K.; Araki, T.
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 150, Issue 2-3
Is there a molecular analogue of a Kondo singlet state?
journal, September 1989
- Neumann, C. S.; Fulde, P.
- Zeitschrift f�r Physik B Condensed Matter, Vol. 74, Issue 3
Energy-Degeneracy-Driven Covalency in Actinide Bonding
journal, December 2018
- Su, Jing; Batista, Enrique R.; Boland, Kevin S.
- Journal of the American Chemical Society, Vol. 140, Issue 51
Ab Initio Ligand-Field Theory Analysis and Covalency Trends in Actinide and Lanthanide Free Ions and Octahedral Complexes
journal, July 2017
- Jung, Julie; Atanasov, Mihail; Neese, Frank
- Inorganic Chemistry, Vol. 56, Issue 15
Bonding and Charge Transfer in Nitrogen-Donor Uranyl Complexes: Insights from NEXAFS Spectra
journal, October 2014
- Pemmaraju, C. D.; Copping, Roy; Wang, Shuao
- Inorganic Chemistry, Vol. 53, Issue 21
Spectrum analysis of U 3+ :LaCl 3
journal, May 1980
- Crosswhite, H. M.; Crosswhite, H.; Carnall, W. T.
- The Journal of Chemical Physics, Vol. 72, Issue 9
An Efficient Access to Organocerium(IV) Complexes: Synthesis and Structure of Bis[1,3,6-tris(trimethylsilyl)cyclooctatetraene]cerium(IV)
journal, September 1994
- Kilimann, Ulrike; Herbst-Irmer, Regine; Stalke, Dietmar
- Angewandte Chemie International Edition in English, Vol. 33, Issue 1516
All-electron CASPT2 study of Ce(η8–C8H6)2
journal, June 2010
- Kerridge, Andrew; Kaltsoyannis, Nikolas
- Comptes Rendus Chimie, Vol. 13, Issue 6-7
Uranocenes with hydrocarbon substituents
journal, May 1973
- Streitwieser, A.; Harmon, C. A.
- Inorganic Chemistry, Vol. 12, Issue 5
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
Scrutinizing metal–ligand covalency and redox non-innocence via nitrogen K-edge X-ray absorption spectroscopy
journal, January 2019
- Lukens, James T.; DiMucci, Ida M.; Kurogi, Takashi
- Chemical Science, Vol. 10, Issue 19
Works referencing / citing this record:
Dysprosiacarboranes as Organometallic Single‐Molecule Magnets
journal, March 2020
- Jin, Peng‐Bo; Zhai, Yuan‐Qi; Yu, Ke‐Xin
- Angewandte Chemie International Edition, Vol. 59, Issue 24
Comparison of tetravalent cerium and terbium ions in a conserved, homoleptic imidophosphorane ligand field
journal, January 2020
- Rice, Natalie T.; Popov, Ivan A.; Russo, Dominic R.
- Chemical Science, Vol. 11, Issue 24