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

Abstract

L{sub 2,3}-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-[Ru{sub 2}{sup III}O(H{sub 2}O){sub 2}(bpy){sub 4}]{sup 4+} water oxidation catalyst. Spectra of the blue dimer and the monomeric [Ru(NH{sub 3}){sub 6}]{sup 3+} model complex show considerably different splitting of the Ru L{sub 2,3} 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{sub 2,3}-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{sub 2,3}-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(NH{sub 3}){sub 6}]{sup 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.more » 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

Authors:
; ; ; ; ; ; ;  [1]
  1. UNC
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
DOE - BASIC ENERGY SCIENCESUNIVERSITY
OSTI Identifier:
1025648
Resource Type:
Journal Article
Journal Name:
J. Am. Chem. Soc.
Additional Journal Information:
Journal Volume: 133; Journal Issue: (39) ; 10, 2011; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Alperovich, Igor, Smolentsev, Grigory, Moonshiram, Dooshaye, Jurss, Jonah W., Concepcion, Javier J., Meyer, Thomas J., Soldatov, Alexander, Pushkar, Yulia, Purdue), SFU-Russia), and Lund). Understanding the Electronic Structure of 4d Metal Complexes: From Molecular Spinors to L-Edge Spectra of a di-Ru Catalyst. United States: N. p., 2015. Web. doi:10.1021/ja207409q.
Alperovich, Igor, Smolentsev, Grigory, Moonshiram, Dooshaye, Jurss, Jonah W., Concepcion, Javier J., Meyer, Thomas J., Soldatov, Alexander, Pushkar, Yulia, Purdue), SFU-Russia), & Lund). Understanding the Electronic Structure of 4d Metal Complexes: From Molecular Spinors to L-Edge Spectra of a di-Ru Catalyst. United States. https://doi.org/10.1021/ja207409q
Alperovich, Igor, Smolentsev, Grigory, Moonshiram, Dooshaye, Jurss, Jonah W., Concepcion, Javier J., Meyer, Thomas J., Soldatov, Alexander, Pushkar, Yulia, Purdue), SFU-Russia), and Lund). 2015. "Understanding the Electronic Structure of 4d Metal Complexes: From Molecular Spinors to L-Edge Spectra of a di-Ru Catalyst". United States. https://doi.org/10.1021/ja207409q.
@article{osti_1025648,
title = {Understanding the Electronic Structure of 4d Metal Complexes: From Molecular Spinors to L-Edge Spectra of a di-Ru Catalyst},
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 and Purdue) and SFU-Russia) and Lund)},
abstractNote = {L{sub 2,3}-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-[Ru{sub 2}{sup III}O(H{sub 2}O){sub 2}(bpy){sub 4}]{sup 4+} water oxidation catalyst. Spectra of the blue dimer and the monomeric [Ru(NH{sub 3}){sub 6}]{sup 3+} model complex show considerably different splitting of the Ru L{sub 2,3} 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{sub 2,3}-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{sub 2,3}-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(NH{sub 3}){sub 6}]{sup 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.},
doi = {10.1021/ja207409q},
url = {https://www.osti.gov/biblio/1025648}, journal = {J. Am. Chem. Soc.},
issn = {0002-7863},
number = (39) ; 10, 2011,
volume = 133,
place = {United States},
year = {Thu Sep 17 00:00:00 EDT 2015},
month = {Thu Sep 17 00:00:00 EDT 2015}
}