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Title: Electronic Structure and Properties of Berkelium Iodates

Abstract

The reaction of 249Bk(OH)4 with iodate under hydrothermal conditions results in the formation of Bk(IO3)3 as the major product with trace amounts of Bk(IO3)4 also crystallizing from the reaction mixture. The structure of Bk(IO3)3 consists of nine-coordinate BkIII cations that are bridged by iodate anions to yield layers that are isomorphous with those found for AmIII, CfIII, and with lanthanides that possess similar ionic radii. Bk(IO3)4 was expected to adopt the same structure as M(IO3)4 (M = Ce, Np, Pu), but instead parallels the structural chemistry of the smaller ZrIV cation. BkIII–O and BkIV–O bond lengths are shorter than anticipated and provide further support for a postcurium break in the actinide series. Photoluminescence and absorption spectra collected from single crystals of Bk(IO3)4 show evidence for doping with BkIII in these crystals. In addition to luminescence from BkIII in the Bk(IO3)4 crystals, a broad-band absorption feature is initially present that is similar to features observed in systems with intervalence charge transfer. However, the high-specific activity of 249Bk (t1/2 = 320 d) causes oxidation of BkIII and only BkIV is present after a few days with concomitant loss of both the BkIII luminescence and the broadband feature. The electronic structure of Bk(IO3)3more » and Bk(IO3)4 were examined using a range of computational methods that include density functional theory both on clusters and on periodic structures, relativistic ab initio wave function calculations that incorporate spin–orbit coupling (CASSCF), and by a full-model Hamiltonian with spin–orbit coupling and Slater–Condon parameters (CONDON). Some of these methods provide evidence for an asymmetric ground state present in BkIV that does not strictly adhere to Russel–Saunders coupling and Hund’s Rule even though it possesses a half-filled 5f 7 shell. Multiple factors contribute to the asymmetry that include 5f electrons being present in microstates that are not solely spin up, spin–orbit coupling induced mixing of low-lying excited states with the ground state, and covalency in the BkIV–O bonds that distributes the 5f electrons onto the ligands. These factors are absent or diminished in other f7 ions such as GdIII or CmIII.« less

Authors:
 [1];  [1];  [2];  [3];  [1];  [1];  [3];  [4];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [4];  [1]; ORCiD logo [1];  [5] more »; ORCiD logo [6]; ORCiD logo [6];  [2]; ORCiD logo [7];  [8]; ORCiD logo [8]; ORCiD logo [9]; ORCiD logo [9];  [9];  [10]; ORCiD logo [1] « less
+ Show Author Affiliations
  1. Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States
  2. Department of Chemistry, Rice University, Houston, Texas 77251, United States
  3. National High Magnetic Field Laboratory, Tallahassee, Florida 32310, United States
  4. Environmental Health and Safety, Florida State University, Tallahassee, Florida 32306, United States
  5. Nuclear Materials Processing Group, Oak Ridge National Laboratory, One Bethel Valley Road, Oak Ridge, Tennessee 37830, United States
  6. Department of Chemistry, University at Buffalo, State University of New York, Buffalo, New York 14260, United States
  7. Laboratorie de Physique et Chimie des Nano-objets, Institut National des Sciences Appliquées, 31077 Toulouse Cedex 4, France
  8. Institut für Anorganische Chemie, RWTH Aachen University, D-52074 Aachen, Germany
  9. Centro de Nanociencias Aplicadas, Facultad de Ciencias Exactas, Universidad Andrés Bello, República 275, Santiago, Chile
  10. Bruker AXS, 5465 East Cheryl Parkway, Madison, Wisconsin 53711, United States
Publication Date:
Research Org.:
Florida State Univ., Tallahassee, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1399633
Alternate Identifier(s):
OSTI ID: 1508262
Grant/Contract Number:  
FG02-04ER15523; FG02-13ER16414; SC0001136; SC0010677
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 139 Journal Issue: 38; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Silver, Mark A., Cary, Samantha K., Garza, Alejandro J., Baumbach, Ryan E., Arico, Alexandra A., Galmin, Gregory A., Chen, Kuan-Wen, Johnson, Jason A., Wang, Jamie C., Clark, Ronald J., Chemey, Alexander, Eaton, Teresa M., Marsh, Matthew L., Seidler, Kevin, Galley, Shane S., van de Burgt, Lambertus, Gray, Ashley L., Hobart, David E., Hanson, Kenneth, Van Cleve, Shelley M., Gendron, Frédéric, Autschbach, Jochen, Scuseria, Gustavo E., Maron, Laurent, Speldrich, Manfred, Kögerler, Paul, Celis-Barros, Cristian, Páez-Hernández, Dayán, Arratia-Pérez, Ramiro, Ruf, Michael, and Albrecht-Schmitt, Thomas E. Electronic Structure and Properties of Berkelium Iodates. United States: N. p., 2017. Web. doi:10.1021/jacs.7b05569.
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Silver, Mark A., Cary, Samantha K., Garza, Alejandro J., Baumbach, Ryan E., Arico, Alexandra A., Galmin, Gregory A., Chen, Kuan-Wen, Johnson, Jason A., Wang, Jamie C., Clark, Ronald J., Chemey, Alexander, Eaton, Teresa M., Marsh, Matthew L., Seidler, Kevin, Galley, Shane S., van de Burgt, Lambertus, Gray, Ashley L., Hobart, David E., Hanson, Kenneth, Van Cleve, Shelley M., Gendron, Frédéric, Autschbach, Jochen, Scuseria, Gustavo E., Maron, Laurent, Speldrich, Manfred, Kögerler, Paul, Celis-Barros, Cristian, Páez-Hernández, Dayán, Arratia-Pérez, Ramiro, Ruf, Michael, & Albrecht-Schmitt, Thomas E. Electronic Structure and Properties of Berkelium Iodates. United States. https://doi.org/10.1021/jacs.7b05569
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Silver, Mark A., Cary, Samantha K., Garza, Alejandro J., Baumbach, Ryan E., Arico, Alexandra A., Galmin, Gregory A., Chen, Kuan-Wen, Johnson, Jason A., Wang, Jamie C., Clark, Ronald J., Chemey, Alexander, Eaton, Teresa M., Marsh, Matthew L., Seidler, Kevin, Galley, Shane S., van de Burgt, Lambertus, Gray, Ashley L., Hobart, David E., Hanson, Kenneth, Van Cleve, Shelley M., Gendron, Frédéric, Autschbach, Jochen, Scuseria, Gustavo E., Maron, Laurent, Speldrich, Manfred, Kögerler, Paul, Celis-Barros, Cristian, Páez-Hernández, Dayán, Arratia-Pérez, Ramiro, Ruf, Michael, and Albrecht-Schmitt, Thomas E. Thu . "Electronic Structure and Properties of Berkelium Iodates". United States. https://doi.org/10.1021/jacs.7b05569.
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@article{osti_1399633,
title = {Electronic Structure and Properties of Berkelium Iodates},
author = {Silver, Mark A. and Cary, Samantha K. and Garza, Alejandro J. and Baumbach, Ryan E. and Arico, Alexandra A. and Galmin, Gregory A. and Chen, Kuan-Wen and Johnson, Jason A. and Wang, Jamie C. and Clark, Ronald J. and Chemey, Alexander and Eaton, Teresa M. and Marsh, Matthew L. and Seidler, Kevin and Galley, Shane S. and van de Burgt, Lambertus and Gray, Ashley L. and Hobart, David E. and Hanson, Kenneth and Van Cleve, Shelley M. and Gendron, Frédéric and Autschbach, Jochen and Scuseria, Gustavo E. and Maron, Laurent and Speldrich, Manfred and Kögerler, Paul and Celis-Barros, Cristian and Páez-Hernández, Dayán and Arratia-Pérez, Ramiro and Ruf, Michael and Albrecht-Schmitt, Thomas E.},
abstractNote = {The reaction of 249Bk(OH)4 with iodate under hydrothermal conditions results in the formation of Bk(IO3)3 as the major product with trace amounts of Bk(IO3)4 also crystallizing from the reaction mixture. The structure of Bk(IO3)3 consists of nine-coordinate BkIII cations that are bridged by iodate anions to yield layers that are isomorphous with those found for AmIII, CfIII, and with lanthanides that possess similar ionic radii. Bk(IO3)4 was expected to adopt the same structure as M(IO3)4 (M = Ce, Np, Pu), but instead parallels the structural chemistry of the smaller ZrIV cation. BkIII–O and BkIV–O bond lengths are shorter than anticipated and provide further support for a postcurium break in the actinide series. Photoluminescence and absorption spectra collected from single crystals of Bk(IO3)4 show evidence for doping with BkIII in these crystals. In addition to luminescence from BkIII in the Bk(IO3)4 crystals, a broad-band absorption feature is initially present that is similar to features observed in systems with intervalence charge transfer. However, the high-specific activity of 249Bk (t1/2 = 320 d) causes oxidation of BkIII and only BkIV is present after a few days with concomitant loss of both the BkIII luminescence and the broadband feature. The electronic structure of Bk(IO3)3 and Bk(IO3)4 were examined using a range of computational methods that include density functional theory both on clusters and on periodic structures, relativistic ab initio wave function calculations that incorporate spin–orbit coupling (CASSCF), and by a full-model Hamiltonian with spin–orbit coupling and Slater–Condon parameters (CONDON). Some of these methods provide evidence for an asymmetric ground state present in BkIV that does not strictly adhere to Russel–Saunders coupling and Hund’s Rule even though it possesses a half-filled 5f 7 shell. Multiple factors contribute to the asymmetry that include 5f electrons being present in microstates that are not solely spin up, spin–orbit coupling induced mixing of low-lying excited states with the ground state, and covalency in the BkIV–O bonds that distributes the 5f electrons onto the ligands. These factors are absent or diminished in other f7 ions such as GdIII or CmIII.},
doi = {10.1021/jacs.7b05569},
journal = {Journal of the American Chemical Society},
number = 38,
volume = 139,
place = {United States},
year = {Thu Sep 14 00:00:00 EDT 2017},
month = {Thu Sep 14 00:00:00 EDT 2017}
}
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Monomers, Dimers, and Helices: Complexities of Cerium and Plutonium Phenanthrolinecarboxylates
journal, April 2016

Computerized magnetic studies on d, f, d–d, f–f, and d–S, f–S systems under varying ligand and magnetic fields
journal, October 2004

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

Laser induced fluorescence of 249Bk4+ in CeF4
journal, December 1987

Novel heptavalent actinide compounds: tetrasodium dihydroxidotetraoxidoneptunate(VII) hydroxide dihydrate and its plutonium analogue
journal, November 2009

  • Grigoriev, Mikhail S.; Krot, Nikolai N.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 65, Issue 12
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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
  • DOI: 10.1063/1.464913

The crystal structure of Zr(IO3)4
journal, February 1961

Structure validation in chemical crystallography
journal, January 2009

  • Spek, Anthony L.
  • Acta Crystallographica Section D Biological Crystallography, Vol. 65, Issue 2, p. 148-155
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A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach
journal, May 1980

Multiwfn: A multifunctional wavefunction analyzer
journal, December 2011

  • Lu, Tian; Chen, Feiwu
  • Journal of Computational Chemistry, Vol. 33, Issue 5
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The influence of polarization functions on molecular orbital hydrogenation energies
journal, January 1973

  • Hariharan, P. C.; Pople, J. A.
  • Theoretica Chimica Acta, Vol. 28, Issue 3
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Predicting Band Gaps with Hybrid Density Functionals
journal, October 2016

  • Garza, Alejandro J.; Scuseria, Gustavo E.
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 20
  • DOI: 10.1021/acs.jpclett.6b01807

Periodic Trends in Lanthanide and Actinide Phosphonates: Discontinuity between Plutonium and Americium
journal, June 2012

  • Diwu, Juan; Grant, Daniel J.; Wang, Shuao
  • Inorganic Chemistry, Vol. 51, Issue 12
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Unusual structure, bonding and properties in a californium borate
journal, March 2014

  • Polinski, Matthew J.; Garner, Edward B.; Maurice, Rémi
  • Nature Chemistry, Vol. 6, Issue 5
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Atomistic calculations of the thermodynamic properties of mixing for tetravalent metal dioxide solid solutions: (Zr, Th, Ce)O2
journal, January 2013

Natural hybrid orbitals
journal, September 1980

  • Foster, J. P.; Weinhold, F.
  • Journal of the American Chemical Society, Vol. 102, Issue 24
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The crystal structure of Ce(IO 3 ) 4
journal, December 1956

Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992

The crystal structure of ceric iodate monohydrate
journal, March 1956

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
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The formal potential of the Bk(IV)-Bk(III) couple in several media
journal, January 1972

  • Stokely, J. R.; Baybarz, R. D.; Peterson, J. R.
  • Journal of Inorganic and Nuclear Chemistry, Vol. 34, Issue 1
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Second-order perturbation theory with a CASSCF reference function
journal, July 1990

  • Andersson, Kerstin.; Malmqvist, Per Aake.; Roos, Bjoern O.
  • The Journal of Physical Chemistry, Vol. 94, Issue 14
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Spontaneous Partitioning of Californium from Curium: Curious Cases from the Crystallization of Curium Coordination Complexes
journal, November 2015

Microchemical preparation of tricyclopentadienyl compounds of berkelium, californium, and some lanthanide elements
journal, May 1970

  • Laubereau, Peter G.; Burns, John H.
  • Inorganic Chemistry, Vol. 9, Issue 5
  • DOI: 10.1021/ic50087a018

Heptavalent state of neptunium and plutonium
journal, September 1969

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
  • DOI: 10.1063/1.439742

Mechanisms in coprecipitation of berkelium(IV) with cerium(IV) iodate from homogeneous solution
journal, August 1969

  • Fardy, John J.; Weaver, Boyd.
  • Analytical Chemistry, Vol. 41, Issue 10
  • DOI: 10.1021/ac60279a006

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
  • DOI: 10.1038/nchem.2759
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