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Understanding the Electronic Structure of 4d Metal Complexes: From Molecular Spinors to L-Edge Spectra of a di-Ru Catalyst

Alperovich, Igor; Smolentsev, Grigory LU ; Moonshiram, Dooshaye; Jurss, Jonah W.; Concepcion, Javier J.; Meyer, Thomas J.; Soldatov, Alexander and Pushkar, Yulia (2011) In Journal of the American Chemical Society 133(39). p.15786-15794
Abstract
L-2,L-3-edge X-ray absorption spectroscopy (XAS) has demonstrated unique capabilities for the analysis of the electronic structure of di-Ru complexes such as the blue dimer cis,cis-[(Ru2O)-O-III(H2O)(2)(bpy)(4)](4+) water oxidation catalyst. Spectra of the blue dimer and the monomeric [Ru(NH3)(6)](3+) model complex show considerably different splitting of the Ru L-2,L-3 absorption edge, which reflects changes in the relative energies of the Ru 4d orbitals caused by hybridization with a bridging ligand and spin-orbit coupling effects. To aid the interpretation of spectroscopic data, we developed a new approach, which computes L-2,L-3-edges XAS spectra as dipole transitions between molecular spinors of 4d transition metal complexes. This... (More)
L-2,L-3-edge X-ray absorption spectroscopy (XAS) has demonstrated unique capabilities for the analysis of the electronic structure of di-Ru complexes such as the blue dimer cis,cis-[(Ru2O)-O-III(H2O)(2)(bpy)(4)](4+) water oxidation catalyst. Spectra of the blue dimer and the monomeric [Ru(NH3)(6)](3+) model complex show considerably different splitting of the Ru L-2,L-3 absorption edge, which reflects changes in the relative energies of the Ru 4d orbitals caused by hybridization with a bridging ligand and spin-orbit coupling effects. To aid the interpretation of spectroscopic data, we developed a new approach, which computes L-2,L-3-edges XAS spectra as dipole transitions between molecular spinors of 4d transition metal complexes. This allows for careful inclusion of the spin-orbit coupling effects and the hybridization of the Ru 4d and ligand orbitals. The obtained theoretical Ru L-2,L-3-edge spectra are in close agreement with experiment. Critically, existing single-electron methods (FEFF, FDMNES) broadly used to simulate XAS could not reproduce the experimental Ru L-edge spectra for the [Ru(NH3)(6)](3+) model complex nor for the blue dimer, while charge transfer multiplet (CTM) calculations were not applicable due to the complexity and low symmetry of the blue dimer water oxidation catalyst. We demonstrated that L-edge spectroscopy is informative for analysis of bridging metal complexes. The developed computational approach enhances L-edge spectroscopy as a tool for analysis of the electronic structures of complexes, materials, catalysts, and reactive intermediates with 4d transition metals. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the American Chemical Society
volume
133
issue
39
pages
15786 - 15794
publisher
The American Chemical Society
external identifiers
  • wos:000295911500083
  • scopus:80053300464
ISSN
1520-5126
DOI
10.1021/ja207409q
language
English
LU publication?
yes
id
6174e1f7-12d4-4da5-a9ed-3a558a230d82 (old id 2211788)
date added to LUP
2011-11-30 11:12:53
date last changed
2017-02-05 03:54:31
@article{6174e1f7-12d4-4da5-a9ed-3a558a230d82,
  abstract     = {L-2,L-3-edge X-ray absorption spectroscopy (XAS) has demonstrated unique capabilities for the analysis of the electronic structure of di-Ru complexes such as the blue dimer cis,cis-[(Ru2O)-O-III(H2O)(2)(bpy)(4)](4+) water oxidation catalyst. Spectra of the blue dimer and the monomeric [Ru(NH3)(6)](3+) model complex show considerably different splitting of the Ru L-2,L-3 absorption edge, which reflects changes in the relative energies of the Ru 4d orbitals caused by hybridization with a bridging ligand and spin-orbit coupling effects. To aid the interpretation of spectroscopic data, we developed a new approach, which computes L-2,L-3-edges XAS spectra as dipole transitions between molecular spinors of 4d transition metal complexes. This allows for careful inclusion of the spin-orbit coupling effects and the hybridization of the Ru 4d and ligand orbitals. The obtained theoretical Ru L-2,L-3-edge spectra are in close agreement with experiment. Critically, existing single-electron methods (FEFF, FDMNES) broadly used to simulate XAS could not reproduce the experimental Ru L-edge spectra for the [Ru(NH3)(6)](3+) model complex nor for the blue dimer, while charge transfer multiplet (CTM) calculations were not applicable due to the complexity and low symmetry of the blue dimer water oxidation catalyst. We demonstrated that L-edge spectroscopy is informative for analysis of bridging metal complexes. The developed computational approach enhances L-edge spectroscopy as a tool for analysis of the electronic structures of complexes, materials, catalysts, and reactive intermediates with 4d transition metals.},
  author       = {Alperovich, Igor and Smolentsev, Grigory and Moonshiram, Dooshaye and Jurss, Jonah W. and Concepcion, Javier J. and Meyer, Thomas J. and Soldatov, Alexander and Pushkar, Yulia},
  issn         = {1520-5126},
  language     = {eng},
  number       = {39},
  pages        = {15786--15794},
  publisher    = {The American Chemical Society},
  series       = {Journal of the American Chemical Society},
  title        = {Understanding the Electronic Structure of 4d Metal Complexes: From Molecular Spinors to L-Edge Spectra of a di-Ru Catalyst},
  url          = {http://dx.doi.org/10.1021/ja207409q},
  volume       = {133},
  year         = {2011},
}