Distorted Tetrahedral CoII in K5H[CoW12O40]·xH2O Probed by 2p3d Resonant Inelastic X-ray Scattering

LIU BY Liu; Ru Pan Wang; Elliot N. Glass; Craig L. Hill; Tanja Cuk; Jun Okamoto; Di Jing Huang; Matti M. Van Schooneveld; Frank M F De Groot

doi:10.1021/acs.inorgchem.6b01228

Distorted Tetrahedral Co^II in K₅H[CoW₁₂O₄₀]·xH₂O Probed by 2p3d Resonant Inelastic X-ray Scattering

LIU BY Liu, Ru Pan Wang, Elliot N. Glass, Craig L. Hill, Tanja Cuk, Jun Okamoto, Di Jing Huang, Matti M. Van Schooneveld^*, Frank M F De Groot

^*Corresponding author for this work

Research output: Contribution to journal › Article › Academic › peer-review

Abstract

The Co 2p_3/2 X-ray absorption spectroscopy and high-energy-resolution (∼0.09 eV fwhm) 2p3d resonant inelastic X-ray scattering (RIXS) spectra of the single-cobalt-centered polyoxometalate K₅H[CoW₁₂O₄₀]·xH₂O were measured. The low-energy dd transition features at 0.55 eV, unmeasurable with ultraviolet-visible (UV/vis) spectroscopy, were experimentally revealed in 2p3d RIXS spectra. RIXS simulations based on ligand-field multiplet theory were performed to assess the potential cobalt tetragonal symmetry distortion, which is described with the ligand-field parameters 10D_q (-0.54 eV), D_s (-0.08 eV), and D_t (0.005 eV). Because 2p3d RIXS probes not only the optical spin-allowed transitions but also the spin-forbidden transitions, we show that the current 2p3d RIXS simulation enables a series of dd feature assignments with higher accuracy than those from previous optical data. Furthermore, by wave-function decomposition analyses, we demonstrate the more realistic and detailed origins of a few lowest dd transitions using both one-electron-orbital and term-symbol descriptions.

Original language	English
Pages (from-to)	10152-10160
Number of pages	9
Journal	Inorganic Chemistry
Volume	55
Issue number	20
DOIs	https://doi.org/10.1021/acs.inorgchem.6b01228
Publication status	Published - 17 Oct 2016

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@article{1a678246c9714296a5622918e40d4684,

title = "Distorted Tetrahedral CoII in K5H[CoW12O40]·xH2O Probed by 2p3d Resonant Inelastic X-ray Scattering",

abstract = "The Co 2p3/2 X-ray absorption spectroscopy and high-energy-resolution (∼0.09 eV fwhm) 2p3d resonant inelastic X-ray scattering (RIXS) spectra of the single-cobalt-centered polyoxometalate K5H[CoW12O40]·xH2O were measured. The low-energy dd transition features at 0.55 eV, unmeasurable with ultraviolet-visible (UV/vis) spectroscopy, were experimentally revealed in 2p3d RIXS spectra. RIXS simulations based on ligand-field multiplet theory were performed to assess the potential cobalt tetragonal symmetry distortion, which is described with the ligand-field parameters 10Dq (-0.54 eV), Ds (-0.08 eV), and Dt (0.005 eV). Because 2p3d RIXS probes not only the optical spin-allowed transitions but also the spin-forbidden transitions, we show that the current 2p3d RIXS simulation enables a series of dd feature assignments with higher accuracy than those from previous optical data. Furthermore, by wave-function decomposition analyses, we demonstrate the more realistic and detailed origins of a few lowest dd transitions using both one-electron-orbital and term-symbol descriptions.",

author = "Liu, {LIU BY} and Wang, {Ru Pan} and Glass, {Elliot N.} and Hill, {Craig L.} and Tanja Cuk and Jun Okamoto and Huang, {Di Jing} and {Van Schooneveld}, {Matti M.} and {De Groot}, {Frank M F}",

year = "2016",

month = oct,

day = "17",

doi = "10.1021/acs.inorgchem.6b01228",

language = "English",

volume = "55",

pages = "10152--10160",

journal = "Inorganic Chemistry",

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T1 - Distorted Tetrahedral CoII in K5H[CoW12O40]·xH2O Probed by 2p3d Resonant Inelastic X-ray Scattering

AU - Liu, LIU BY

AU - Wang, Ru Pan

AU - Glass, Elliot N.

AU - Hill, Craig L.

AU - Cuk, Tanja

AU - Okamoto, Jun

AU - Huang, Di Jing

AU - Van Schooneveld, Matti M.

AU - De Groot, Frank M F

PY - 2016/10/17

Y1 - 2016/10/17

N2 - The Co 2p3/2 X-ray absorption spectroscopy and high-energy-resolution (∼0.09 eV fwhm) 2p3d resonant inelastic X-ray scattering (RIXS) spectra of the single-cobalt-centered polyoxometalate K5H[CoW12O40]·xH2O were measured. The low-energy dd transition features at 0.55 eV, unmeasurable with ultraviolet-visible (UV/vis) spectroscopy, were experimentally revealed in 2p3d RIXS spectra. RIXS simulations based on ligand-field multiplet theory were performed to assess the potential cobalt tetragonal symmetry distortion, which is described with the ligand-field parameters 10Dq (-0.54 eV), Ds (-0.08 eV), and Dt (0.005 eV). Because 2p3d RIXS probes not only the optical spin-allowed transitions but also the spin-forbidden transitions, we show that the current 2p3d RIXS simulation enables a series of dd feature assignments with higher accuracy than those from previous optical data. Furthermore, by wave-function decomposition analyses, we demonstrate the more realistic and detailed origins of a few lowest dd transitions using both one-electron-orbital and term-symbol descriptions.

AB - The Co 2p3/2 X-ray absorption spectroscopy and high-energy-resolution (∼0.09 eV fwhm) 2p3d resonant inelastic X-ray scattering (RIXS) spectra of the single-cobalt-centered polyoxometalate K5H[CoW12O40]·xH2O were measured. The low-energy dd transition features at 0.55 eV, unmeasurable with ultraviolet-visible (UV/vis) spectroscopy, were experimentally revealed in 2p3d RIXS spectra. RIXS simulations based on ligand-field multiplet theory were performed to assess the potential cobalt tetragonal symmetry distortion, which is described with the ligand-field parameters 10Dq (-0.54 eV), Ds (-0.08 eV), and Dt (0.005 eV). Because 2p3d RIXS probes not only the optical spin-allowed transitions but also the spin-forbidden transitions, we show that the current 2p3d RIXS simulation enables a series of dd feature assignments with higher accuracy than those from previous optical data. Furthermore, by wave-function decomposition analyses, we demonstrate the more realistic and detailed origins of a few lowest dd transitions using both one-electron-orbital and term-symbol descriptions.

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Distorted Tetrahedral Co^II in K₅H[CoW₁₂O₄₀]·xH₂O Probed by 2p3d Resonant Inelastic X-ray Scattering

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