Covalency in Lanthanides. An X-ray Absorption Spectroscopy and Density Functional Theory Study of LnCl (x = 3, 2).
Covalency in Ln-Cl bonds of O-LnCl (x = 3 for Ln = Ce, Nd, Sm, Eu, Gd; x = 2 for Ln = Ce) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L-edge and M-edge XAS were also used to characterize...
| Publicado en: | Journal of the American Chemical Society Vol. 137; no. 7; pp. 2506 - 2524 |
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| Autores principales: | , , , , , , , , , , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
2/25/2015
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=101510143&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 101510143 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 2/25/2015 vid: 137 iid: 7 pid: 997 pub: American Chemical Society artinfo: ui: 101510143 10.1021/ja510067v ppf: 2506 ppct: 18 formats: tig: atl: Covalency in Lanthanides. An X-ray Absorption Spectroscopy and Density Functional Theory Study of LnCl (x = 3, 2). aug: au: Löble, Matthias W. Keith, Jason M. Altman, Alison B. Stieber, S. Chantal E. Batista, Enrique R. Boland, Kevin S. Conradson, Steven D. Clark, David L. Pacheco, Juan Lezama Kozimor, Stosh A. Martin, Richard L. Minasian, Stefan G. Olson, Angela C. Scott, Brian L. Shuh, David K. Tyliszczak, Tolek Wilkerson, Marianne P. Zehnder, Ralph A. affil: Los Alamos National Laboratory, Los Alamos, New Mexico 87545, United States Colgate University, Hamilton, New York 13346, United States University of California, Berkeley, California 94720, United States Stanford University, Stanford, California 94305, United States Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States Angelo State University, San Angelo, Texas 76909, United States su: Rare earth metals Desorption Oxidation states Fluid dynamics Radiation absorption sug: subj: Rare earth metals Desorption Oxidation states Fluid dynamics Radiation absorption ab: Covalency in Ln-Cl bonds of O-LnCl (x = 3 for Ln = Ce, Nd, Sm, Eu, Gd; x = 2 for Ln = Ce) anions has been investigated, primarily using Cl K-edge X-ray absorption spectroscopy (XAS) and time-dependent density functional theory (TDDFT); however, Ce L-edge and M-edge XAS were also used to characterize CeCl (x = 2, 3). The M-edge XAS spectra were modeled using configuration interaction calculations. The results were evaluated as a function of (1) the lanthanide (Ln) metal identity, which was varied across the series from Ce to Gd, and (2) the Ln oxidation state (when practical, i.e., formally Ce and Ce). Pronounced mixing between the Cl 3p- and Ln 5d-orbitals (t* and e*) was observed. Experimental results indicated that Ln 5d-orbital mixing decreased when moving across the lanthanide series. In contrast, oxidizing Ce to Ce had little effect on Cl 3p and Ce 5d-orbital mixing. For LnCl (formally Ln), the 4f-orbitals participated only marginally in covalent bonding, which was consistent with historical descriptions. Surprisingly, there was a marked increase in Cl 3p- and Ce 4f-orbital mixing (t* + t*) in CeCl. This unexpected 4f- and 5d-orbital participation in covalent bonding is presented in the context of recent studies on both tetravalent transition metal and actinide hexahalides, MCl (M = Ti, Zr, Hf, U). pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2015 holdings: @attributes: islocal: N |
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