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Title: The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory

Abstract

Multi-edge soft X-ray absorption spectroscopy is used to probe orbital mixing in actinide and lanthanide Prussian blue analogs.

Authors:
 [1];  [1];  [1];  [2];  [1];  [1];  [3];  [3];  [4]
  1. CEA, Bagnols-sur-Ceze (France)
  2. Helmholtz Zentrum Dresden-Rossendorf, Dresden (Germany)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. CEA, Bagnols-sur-Ceze (France); Univ. of Nice Sophia Antipolis, Nice (France)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
SC-22.1 USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1436132
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 18; Journal Issue: 4; Related Information: © the Owner Societies 2016.; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Dumas, Thomas, Guillaumont, Dominique, Fillaux, Clara, Scheinost, Andreas, Moisy, Philippe, Petit, Sebastien, Shuh, David K., Tyliszczak, Tolek, and Auwer, Christophe Den. The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory. United States: N. p., 2015. Web. doi:10.1039/c5cp05820a.
Dumas, Thomas, Guillaumont, Dominique, Fillaux, Clara, Scheinost, Andreas, Moisy, Philippe, Petit, Sebastien, Shuh, David K., Tyliszczak, Tolek, & Auwer, Christophe Den. The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory. United States. doi:10.1039/c5cp05820a.
Dumas, Thomas, Guillaumont, Dominique, Fillaux, Clara, Scheinost, Andreas, Moisy, Philippe, Petit, Sebastien, Shuh, David K., Tyliszczak, Tolek, and Auwer, Christophe Den. Wed . "The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory". United States. doi:10.1039/c5cp05820a. https://www.osti.gov/servlets/purl/1436132.
@article{osti_1436132,
title = {The nature of chemical bonding in actinide and lanthanide ferrocyanides determined by X-ray absorption spectroscopy and density functional theory},
author = {Dumas, Thomas and Guillaumont, Dominique and Fillaux, Clara and Scheinost, Andreas and Moisy, Philippe and Petit, Sebastien and Shuh, David K. and Tyliszczak, Tolek and Auwer, Christophe Den},
abstractNote = {Multi-edge soft X-ray absorption spectroscopy is used to probe orbital mixing in actinide and lanthanide Prussian blue analogs.},
doi = {10.1039/c5cp05820a},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 4,
volume = 18,
place = {United States},
year = {2015},
month = {12}
}

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Cited by: 8 works
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Works referenced in this record:

Temperature and Light Induced Bistability in a Co 3 [Os(CN) 6 ] 2 6H 2 O Prussian Blue Analog
journal, September 2010

  • Avendano, Carolina; Hilfiger, Matthew G.; Prosvirin, Andrey
  • Journal of the American Chemical Society, Vol. 132, Issue 38
  • DOI: 10.1021/ja1041513

Characterization of Chemical Bonds in Bimetallic Cyanides Using X-ray Absorption Spectroscopy at L 2,3 Edges
journal, January 1996

  • Arrio, M. -A.; Sainctavit, Ph.; Cartier dit Moulin, Ch.
  • Journal of the American Chemical Society, Vol. 118, Issue 27
  • DOI: 10.1021/ja9542698

Possible F-Shell Covalency in the Actinide Elements
journal, April 1950

  • Glueckauf, E.; McKAY, H. A. C.
  • Nature, Vol. 165, Issue 4198
  • DOI: 10.1038/165594a0

Local Structure in Americium and Californium Hexacyanoferrates - Comparison with Their Lanthanide Analogues
journal, February 2011

  • Dupouy, Gaelle; Bonhoure, Isabelle; Conradson, Steven D.
  • European Journal of Inorganic Chemistry, Vol. 2011, Issue 10
  • DOI: 10.1002/ejic.201001004

X-ray absorption near-edge structure calculations beyond the muffin-tin approximation
journal, March 2001


Photoinduced Ferrimagnetic Systems in Prussian Blue Analogues C I x Co 4 [Fe(CN) 6 ] y (C I = Alkali Cation). 2. X-ray Absorption Spectroscopy of the Metastable State
journal, July 2000

  • Cartier dit Moulin, Christophe; Villain, Françoise; Bleuzen, Anne
  • Journal of the American Chemical Society, Vol. 122, Issue 28
  • DOI: 10.1021/ja000349m

Covalency in the f Element−Chalcogen Bond. Computational Studies of M[N(EPR 2 ) 2 ] 3 (M = La, Ce, Pr, Pm, Eu, U, Np, Pu, Am, Cm; E = O, S, Se, Te; R = H, i Pr, Ph)
journal, September 2008

  • Ingram, Kieran I. M.; Tassell, Matthew J.; Gaunt, Andrew J.
  • Inorganic Chemistry, Vol. 47, Issue 17
  • DOI: 10.1021/ic800835k

The strength of actinide–element bonds from the quantum theory of atoms-in-molecules
journal, January 2015

  • Huang, Qian-Rui; Kingham, Jennifer R.; Kaltsoyannis, Nikolas
  • Dalton Transactions, Vol. 44, Issue 6
  • DOI: 10.1039/C4DT02323D

The Separation of Americium and Curium from the Rare Earth Elements
journal, June 1950

  • Street, Kenneth; Seaborg, Glenn T.
  • Journal of the American Chemical Society, Vol. 72, Issue 6
  • DOI: 10.1021/ja01162a530

Soft X-ray scanning transmission X-ray microscopy (STXM) of actinide particles
journal, July 2005

  • Nilsson, Hans J.; Tyliszczak, Tolek; Wilson, Richard E.
  • Analytical and Bioanalytical Chemistry, Vol. 383, Issue 1
  • DOI: 10.1007/s00216-005-3355-5

Metal-to-ligand and ligand-to-metal charge transfer in thin films of Prussian blue analogues investigated by X-ray absorption spectroscopy
journal, January 2008

  • Bonhommeau, Sébastien; Pontius, Niko; Cobo, Saioa
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 38
  • DOI: 10.1039/b806783j

Pressure-Induced Magnetic Switching and Linkage Isomerism in K 0.4 Fe 4 [Cr(CN) 6 ] 2.8 ·16H 2 O: X-ray Absorption and Magnetic Circular Dichroism Studies
journal, November 2008

  • Coronado, Eugenio; Giménez-López, M. Carmen; Korzeniak, Tomasz
  • Journal of the American Chemical Society, Vol. 130, Issue 46
  • DOI: 10.1021/ja8047046

Multi-edge X-ray absorption spectroscopy of thorium, neptunium and plutonium hexacyanoferrate compounds
journal, January 2013

  • Dumas, Thomas; Charbonnel, Marie Christine; Charushnikova, Iraida A.
  • New Journal of Chemistry, Vol. 37, Issue 10
  • DOI: 10.1039/c3nj00318c

X-ray absorption edge spectroscopy of ligands bound to open-shell metal ions: chlorine K-edge studies of covalency in tetrachlorocuprate(2-)
journal, February 1990

  • Hedman, Britt; Hodgson, Keith O.; Solomon, Edward I.
  • Journal of the American Chemical Society, Vol. 112, Issue 4
  • DOI: 10.1021/ja00160a062

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
  • DOI: 10.1039/C3SC52030G

Chemistry with ADF
journal, January 2001

  • te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967
  • DOI: 10.1002/jcc.1056

An Inclusion Complex of Uranyl in a Diazacrown: (Diaza-18-crown-6)2+.2CF3SO3− and [UO2(diaza-18-crown-6)]+.CF3SO3−
journal, May 1995

  • Thuéry, P.; Keller, N.; Lance, M.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 51, Issue 5
  • DOI: 10.1107/S0108270194006037

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)
journal, January 2008

  • Gaunt, Andrew J.; Reilly, Sean D.; Enriquez, Alejandro E.
  • Inorganic Chemistry, Vol. 47, Issue 1
  • DOI: 10.1021/ic701618a

Unique crown thioether complexes of f elements: the crystal structure of U(iii) and La(iii) complexes of 1,4,7-trithiacyclononane
journal, February 2002

  • Karmazin, Lydia; Mazzanti, Marinella; Pécaut, Jacques
  • Chemical Communications, Issue 6
  • DOI: 10.1039/b200315p

The Color and Electronic Configurations of Prussian Blue
journal, May 1962


X-ray absorption spectroscopic studies of the blue copper site: metal and ligand K-edge studies to probe the origin of the EPR hyperfine splitting in plastocyanin
journal, January 1993

  • Shadle, Susan E.; Penner-Hahn, James E.; Schugar, Harvey J.
  • Journal of the American Chemical Society, Vol. 115, Issue 2
  • DOI: 10.1021/ja00055a057

Combining theoretical chemistry and XANES multi-edge experiments to probe actinide valence states
journal, October 2007

  • Fillaux, Clara; Berthet, Jean-Claude; Conradson, Steven D.
  • Comptes Rendus Chimie, Vol. 10, Issue 10-11
  • DOI: 10.1016/j.crci.2006.12.012

Crystal structures of (MeC5H4)3ML [M = uranium or cerium; L = quinuclidine or P(OCH2)3CEt]. Evidence for uranium to phosphorus .pi.-back-bonding
journal, June 1988

  • Brennan, John G.; Stults, Stephen D.; Andersen, Richard A.
  • Organometallics, Vol. 7, Issue 6
  • DOI: 10.1021/om00096a016

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
  • DOI: 10.1021/ic00097a009

Electronic Structure and Bonding in Actinyl Ions and their Analogs
journal, May 2007

  • Denning, Robert G.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 20
  • DOI: 10.1021/jp071061n

Fe L-Edge XAS Studies of K 4 [Fe(CN) 6 ] and K 3 [Fe(CN) 6 ]:  A Direct Probe of Back-Bonding
journal, August 2006

  • Hocking, Rosalie K.; Wasinger, Erik C.; de Groot, Frank M. F.
  • Journal of the American Chemical Society, Vol. 128, Issue 32
  • DOI: 10.1021/ja061802i

Coordination chemistry of lanthanides with emphasis on derivatives with Ln-O-C bonds
journal, January 1980


Solvent Effect of Alcohols at the L-Edge of Iron in Solution: X-ray Absorption and Multiplet Calculations
journal, October 2008

  • Bonhommeau, Sébastien; Ottosson, Niklas; Pokapanich, Wandared
  • The Journal of Physical Chemistry B, Vol. 112, Issue 40
  • DOI: 10.1021/jp8071266

Selectivity of Azine Ligands Toward Lanthanide(III)/Actinide(III) Differentiation: A Relativistic DFT Based Rationalization
journal, April 2014

  • Zaiter, Abdellah; Amine, Boudersa; Bouzidi, Yamina
  • Inorganic Chemistry, Vol. 53, Issue 9
  • DOI: 10.1021/ic500361b

Geometry optimizations in the zero order regular approximation for relativistic effects
journal, May 1999

  • van Lenthe, Erik; Ehlers, Andreas; Baerends, Evert-Jan
  • The Journal of Chemical Physics, Vol. 110, Issue 18
  • DOI: 10.1063/1.478813

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
  • DOI: 10.1021/ja510067v

Trends in Covalency for d- and f-Element Metallocene Dichlorides Identified Using Chlorine K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory
journal, September 2009

  • Kozimor, Stosh A.; Yang, Ping; Batista, Enrique R.
  • Journal of the American Chemical Society, Vol. 131, Issue 34
  • DOI: 10.1021/ja9015759

Control and acquisition systems for new scanning transmission x-ray microscopes at Advanced Light Source (abstract)
journal, March 2002

  • Tyliszczak, T.; Hitchcock, P.; Kilcoyne, A. L. D.
  • Review of Scientific Instruments, Vol. 73, Issue 3
  • DOI: 10.1063/1.1448125

Investigating the electronic structure and bonding in uranyl compounds by combining NEXAFS spectroscopy and quantum chemistry
journal, January 2010

  • Fillaux, Clara; Guillaumont, Dominique; Berthet, Jean-Claude
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 42
  • DOI: 10.1039/c0cp00386g

Natural resonance theory: III. Chemical applications
journal, April 1998


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    Picomolar Traces of Americium(III) Introduce Drastic Changes in the Structural Chemistry of Terbium(III): A Break in the “Gadolinium Break”
    journal, August 2017

    • Welch, Jan M.; Müller, Danny; Knoll, Christian
    • Angewandte Chemie International Edition, Vol. 56, Issue 43
    • DOI: 10.1002/anie.201703971