Electronic Structure and Properties of Berkelium Iodates

Mark A. Silver, Samantha K. Cary, Alejandro J. Garza, Ryan E. Baumbach, Alexandra A. Arico, Gregory A. Galmin, Kuan Wen Chen, Jason A. Johnson, Jamie C. Wang, Ronald J. Clark, Alexander Chemey, Teresa M. Eaton, Matthew L. Marsh, Kevin Seidler, Shane S. Galley, Lambertus Van De Burgt, Ashley L. Gray, David E. Hobart, Kenneth Hanson, Shelley M. Van Cleve & 11 others Frédéric Gendron, Jochen Autschbach, Gustavo E. Scuseria, Laurent Maron, Manfred Speldrich, Paul Kögerler, Cristian Celis-Barros, Dayán Páez-Hernández, Ramiro Arratia-Pérez, Michael Ruf, Thomas E. Albrecht-Schmitt

Research output: Contribution to journalArticle

13 Citations (Scopus)

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)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.

Original languageEnglish
Pages (from-to)13361-13375
Number of pages15
JournalJournal of the American Chemical Society
Volume139
Issue number38
DOIs
Publication statusPublished - 27 Sep 2017

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Berkelium
Iodates
Orbit
Electronic properties
Electronic structure
Orbits
Luminescence
Ground state
Cations
Absorption spectra
Positive ions
Actinoid Series Elements
Electrons
Hamiltonians
Lanthanoid Series Elements
Crystals
Actinides
Periodic structures
Bond length
Wave functions

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Silver, M. A., Cary, S. K., Garza, A. J., Baumbach, R. E., Arico, A. A., Galmin, G. A., ... Albrecht-Schmitt, T. E. (2017). Electronic Structure and Properties of Berkelium Iodates. Journal of the American Chemical Society, 139(38), 13361-13375. https://doi.org/10.1021/jacs.7b05569
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. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 38. pp. 13361-13375.
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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)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.",
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 Alexander Chemey and Eaton, {Teresa M.} and Marsh, {Matthew L.} and Kevin Seidler and Galley, {Shane S.} and {Van De Burgt}, Lambertus and Gray, {Ashley L.} and Hobart, {David E.} and Kenneth Hanson and {Van Cleve}, {Shelley M.} and Fr{\'e}d{\'e}ric Gendron and Jochen Autschbach and Scuseria, {Gustavo E.} and Laurent Maron and Manfred Speldrich and Paul K{\"o}gerler and Cristian Celis-Barros and Day{\'a}n P{\'a}ez-Hern{\'a}ndez and Ramiro Arratia-P{\'e}rez and Michael Ruf and Albrecht-Schmitt, {Thomas E.}",
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Silver, MA, Cary, SK, Garza, AJ, Baumbach, RE, Arico, AA, Galmin, GA, Chen, KW, Johnson, JA, Wang, JC, Clark, RJ, Chemey, A, Eaton, TM, Marsh, ML, Seidler, K, Galley, SS, Van De Burgt, L, Gray, AL, Hobart, DE, Hanson, K, Van Cleve, SM, Gendron, F, Autschbach, J, Scuseria, GE, Maron, L, Speldrich, M, Kögerler, P, Celis-Barros, C, Páez-Hernández, D, Arratia-Pérez, R, Ruf, M & Albrecht-Schmitt, TE 2017, 'Electronic Structure and Properties of Berkelium Iodates', Journal of the American Chemical Society, vol. 139, no. 38, pp. 13361-13375. https://doi.org/10.1021/jacs.7b05569

Electronic Structure and Properties of Berkelium Iodates. / 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.

In: Journal of the American Chemical Society, Vol. 139, No. 38, 27.09.2017, p. 13361-13375.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Electronic Structure and Properties of Berkelium Iodates

AU - Silver, Mark A.

AU - Cary, Samantha K.

AU - Garza, Alejandro J.

AU - Baumbach, Ryan E.

AU - Arico, Alexandra A.

AU - Galmin, Gregory A.

AU - Chen, Kuan Wen

AU - Johnson, Jason A.

AU - Wang, Jamie C.

AU - Clark, Ronald J.

AU - Chemey, Alexander

AU - Eaton, Teresa M.

AU - Marsh, Matthew L.

AU - Seidler, Kevin

AU - Galley, Shane S.

AU - Van De Burgt, Lambertus

AU - Gray, Ashley L.

AU - Hobart, David E.

AU - Hanson, Kenneth

AU - Van Cleve, Shelley M.

AU - Gendron, Frédéric

AU - Autschbach, Jochen

AU - Scuseria, Gustavo E.

AU - Maron, Laurent

AU - Speldrich, Manfred

AU - Kögerler, Paul

AU - Celis-Barros, Cristian

AU - Páez-Hernández, Dayán

AU - Arratia-Pérez, Ramiro

AU - Ruf, Michael

AU - Albrecht-Schmitt, Thomas E.

PY - 2017/9/27

Y1 - 2017/9/27

N2 - 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.

AB - 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.

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U2 - 10.1021/jacs.7b05569

DO - 10.1021/jacs.7b05569

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VL - 139

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EP - 13375

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

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Silver MA, Cary SK, Garza AJ, Baumbach RE, Arico AA, Galmin GA et al. Electronic Structure and Properties of Berkelium Iodates. Journal of the American Chemical Society. 2017 Sep 27;139(38):13361-13375. https://doi.org/10.1021/jacs.7b05569