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Title: The duality of electron localization and covalency in lanthanide and actinide metallocenes

Abstract

Unequivocal experimental evidence for carbon 2p and cerium 4f orbital mixing in cerocene, Ce(C 8 H 8 ) 2 is provided from carbon K-edge and Ce M 5,4 -edge X-ray absorption spectroscopies and corroborated with DFT and configuration interaction calculations.

Authors:
 [1]; ORCiD logo [2];  [1];  [2]; ORCiD logo [3]; ORCiD logo [2];  [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [4];  [1]
  1. Lawrence Berkeley National Laboratory, Berkeley, USA
  2. Los Alamos National Laboratory, Los Alamos, USA
  3. Colgate University, Hamilton, USA
  4. California State Polytechnic University, Pomona, USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1599477
Grant/Contract Number:  
AC02-05CH11231; AC52-06NA25396
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English

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 = {Unequivocal experimental evidence for carbon 2p and cerium 4f orbital mixing in cerocene, Ce(C 8 H 8 ) 2 is provided from carbon K-edge and Ce M 5,4 -edge X-ray absorption spectroscopies and corroborated with DFT and configuration interaction calculations.},
doi = {10.1039/C9SC06114B},
journal = {Chemical Science},
number = ,
volume = ,
place = {United Kingdom},
year = {2020},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1039/C9SC06114B

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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.
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Charge control of the inverse trans-influence
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The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory
journal, January 2016

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Cerium(III) and Cerium(IV) Bis(η 8 -pentalene) Sandwich Complexes:  Synthetic, Structural, Spectroscopic, and Theoretical Studies
journal, June 2007

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New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory
journal, January 2014

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Emergence of the structure-directing role of f-orbital overlap-driven covalency
journal, February 2019


Bis(cyclooctatetraenyl)uranium (uranocene). A new class of sandwich complexes that utilize atomic f orbitals
journal, December 1968

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Photoelectron spectra and bonding in cerocene, bis(.pi.-[8]annulene)cerium(IV)
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Carbon K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory Examination of Metal–Carbon Bonding in Metallocene Dichlorides
journal, September 2013

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The electronic structure of actinide-containing molecules: a challenge to applied quantum chemistry
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A complete basis set model chemistry. II. Open‐shell systems and the total energies of the first‐row atoms
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Ligand K-edge X-ray absorption spectroscopy: covalency of ligand–metal bonds
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The study of actinide chemistry with multiconfigurational quantum chemical methods
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Evidence for 5d-σ and 5d-π covalency in lanthanide sesquioxides from oxygen K-edge X-ray absorption spectroscopy
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A Relativistic Study of the Electronic and Magnetic Properties of Cerocene and Thorocene and Its Anions
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Heavy fermion semiconductors
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A proper account of core-polarization with pseudopotentials: single valence-electron alkali compounds
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Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides
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Covalency in Americium(III) Hexachloride
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Soft X-ray microscopy and spectroscopy at the molecular environmental science beamline at the Advanced Light Source
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Is there a molecular analogue of a Kondo singlet state?
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Energy-Degeneracy-Driven Covalency in Actinide Bonding
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Ab Initio Ligand-Field Theory Analysis and Covalency Trends in Actinide and Lanthanide Free Ions and Octahedral Complexes
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Bonding and Charge Transfer in Nitrogen-Donor Uranyl Complexes: Insights from NEXAFS Spectra
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Spectrum analysis of U 3+ :LaCl 3
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An Efficient Access to Organocerium(IV) Complexes: Synthesis and Structure of Bis[1,3,6-tris(trimethylsilyl)cyclooctatetraene]cerium(IV)
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All-electron CASPT2 study of Ce(η8–C8H6)2
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Uranocenes with hydrocarbon substituents
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Chelation and stabilization of berkelium in oxidation state +IV
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Scrutinizing metal–ligand covalency and redox non-innocence via nitrogen K-edge X-ray absorption spectroscopy
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