Determining Relative f and d Orbital Contributions to M-Cl Covalency in MCl (M = Ti, Zr, Hf, U) and UOCl Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory.
Chlorine K-edge X-ray absorption spectroscopy (XAS) and ground-state and time-dependent hybrid density functional theory (DFT) were used to probe the electronic structures of O-MCl²- (M = Ti, Zr, Hf, U) and C-UOCl-, and to determine the relative contributions of valence 3d, 4d, 5d, 6d, and 5f orbita...
| Publicado en: | Journal of the American Chemical Society Vol. 134; no. 12; pp. 5586 - 5598 |
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| Autores principales: | , , , , , , , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
3/28/2012
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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=74480292&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 74480292 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: 3/28/2012 vid: 134 iid: 12 pid: 997 pub: American Chemical Society artinfo: ui: 74480292 10.1021/ja2105015 ppf: 5586 ppct: 12 formats: tig: atl: Determining Relative f and d Orbital Contributions to M-Cl Covalency in MCl (M = Ti, Zr, Hf, U) and UOCl Using Cl K-Edge X-ray Absorption Spectroscopy and Time-Dependent Density Functional Theory. aug: au: Minasian, Stefan G. Keith, Jason M. Batista, Enrique R. Boland, Kevin S. Clark, David L. Conradson, Steven D. Kozimor, Stosh A. Martin, Richard L. Schwarz, Daniel E. Shuh, David K. Wagner, Gregory L. Wilkerson, Marianne P. Wolfsberg, Laura E. Ping Yang affil: Los Alamos National Laboratory, Los Alamos, New Mexico 8754S, United States Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States W.R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352, United States su: Atomic orbitals Metal complexes Covalent bonds Electronic structure X-ray spectroscopy Density functionals sug: subj: Atomic orbitals Metal complexes Covalent bonds Electronic structure X-ray spectroscopy Density functionals ab: Chlorine K-edge X-ray absorption spectroscopy (XAS) and ground-state and time-dependent hybrid density functional theory (DFT) were used to probe the electronic structures of O-MCl²- (M = Ti, Zr, Hf, U) and C-UOCl-, and to determine the relative contributions of valence 3d, 4d, 5d, 6d, and 5f orbitals in M-Cl bonding. Spectral interpretations were guided by time-dependent DFT calculated transition energies and oscillator strengths, which agree well with the experimental XAS spectra. The data provide new spectroscopic evidence for the involvement of both 5f and 6d orbitals in actinide-ligand bonding in UCl. For the MCl, where transitions into d orbitals of t symmetry are spectroscopically resolved for all four complexes, the experimentally determined Cl 3p character per M-Cl bond increases from 8.3(4)% (TiCl) to 10.3(5)% (ZrCl), 12(1)% (HfCl), and 18(1)% (UCl). Chlorine K-edge XAS spectra of UOCl provide additional insights into the transition assignments by lowering the symmetry to C, where five pre-edge transitions into both 5f and 6d orbitals are observed. For UCl, the XAS data suggest that orbital mixing associated with the U 5f orbitals is considerably lower than that of the U 6d orbitals. For both UCl and UOCl, the ground-state DFT calculations predict a larger 5f contribution to bonding than is determined experimentally. These findings are discussed in the context of conventional theories of covalent bonding for d- and f-block metal complexes. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2012 holdings: @attributes: islocal: N |
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