Electronic Structure and Properties of Berkelium Iodates

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dc.contributor.authorSilver, Mark A.
dc.contributor.authorCary, Samantha K.
dc.contributor.authorGarza, Alejandro J.
dc.contributor.authorBaumbach, Ryan E.
dc.contributor.authorArico, Alexandra A.
dc.contributor.authorGalmin, Gregory A.
dc.contributor.authorChen, Kuan-Wen
dc.contributor.authorJohnson, Jason A.
dc.contributor.authorWang, Jamie C.
dc.contributor.authorClark, Ronald J.
dc.contributor.authorChemey, Alexander
dc.contributor.authorEaton, Teresa M.
dc.contributor.authorMarsh, Matthew L.
dc.contributor.authorSeidler, Kevin
dc.contributor.authorGalley, Shane S.
dc.contributor.authorVan De Burgt, Lambertus
dc.contributor.authorGray, Ashley L.
dc.contributor.authorHobart, David E.
dc.contributor.authorHanson, Kenneth
dc.contributor.authorVan Cleve, Shelley M.
dc.contributor.authorGendron, Frédéric
dc.contributor.authorAutschbach, Jochen
dc.contributor.authorScuseria, Gustavo E.
dc.contributor.authorMaron, Laurent
dc.contributor.authorSpeldrich, Manfred
dc.contributor.authorKögerler, Paul
dc.contributor.authorCelis-Barros, Cristian
dc.contributor.authorPáez-Hernández, Dayán
dc.contributor.authorArratia-Pérez, Ramiro
dc.contributor.authorRuf, Michael
dc.contributor.authorAlbrecht-Schmitt, Thomas E.
dc.date.accessioned2024-03-26T16:19:24Z
dc.date.available2024-03-26T16:19:24Z
dc.date.issued2017-09
dc.descriptionIndexación: Scopus
dc.description.abstractThe 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. © 2017 American Chemical Society.
dc.description.urihttps://pubs-acs-org.recursosbiblioteca.unab.cl/doi/10.1021/jacs.7b05569
dc.identifier.citationJournal of the American Chemical Society Volume 139, Issue 38, Pages 13361 - 1337527 September 2017
dc.identifier.doi10.1021/jacs.7b05569
dc.identifier.issn0002-7863
dc.identifier.urihttps://repositorio.unab.cl/handle/ria/55322
dc.language.isoen
dc.publisherJournal
dc.rights.licenseCC BY 4.0 DEED Atribución 4.0 Internacional
dc.rights.urihttps://creativecommons.org/licenses/by/4.0/deed.es
dc.titleElectronic Structure and Properties of Berkelium Iodates
dc.typeArtículo
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