Electronic structure of tetrahedral iron(III)—sulfur clusters in alkaline thioferrates: an X-ray absorption study

Atanasov, Mihail; Potze, R.; Sawatzky, G. A.

doi:10.1016/0022-4596(95)80056-u

Cited by 15 publications

(9 citation statements)

References 34 publications

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“…The final simulations (solid lines in Figure ) were obtained using the values of U given in Table . It was found that U ≈ 0.8 Q gave the best agreement with the experimental data, which is in good agreement with results for other transition metal systems. − …”

Section: Results and Analysissupporting

confidence: 86%

Electronic Structure Contributions to Electron-Transfer Reactivity in Iron−Sulfur Active Sites: 1. Photoelectron Spectroscopic Determination of Electronic Relaxation

Kennepohl

Solomon

2003

Inorg. Chem.

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Electronic relaxation, the change in molecular electronic structure as a response to oxidation, is investigated in [FeX(4)](2)(-)(,1)(-) (X = Cl, SR) model complexes. Photoelectron spectroscopy, in conjunction with density functional methods, is used to define and evaluate the core and valence electronic relaxation upon ionization of [FeX(4)](2)(-). The presence of intense yet formally forbidden charge-transfer satellite peaks in the PES data is a direct reflection of electronic relaxation. The phenomenon is evaluated as a function of charge redistribution at the metal center (Deltaq(rlx)) resulting from changes in the electronic structure. This charge redistribution is calculated from experimental core and valence PES data using a valence bond configuration interaction (VBCI) model. It is found that electronic relaxation is very large for both core (Fe 2p) and valence (Fe 3d) ionization processes and that it is greater in [Fe(SR)(4)](2)(-) than in [FeCl(4)](2)(-). Similar results are obtained from DFT calculations. The results suggest that, although the lowest-energy valence ionization (from the redox-active molecular orbital) is metal-based, electronic relaxation causes a dramatic redistribution of electron density ( approximately 0.7ē) from the ligands to the metal center corresponding to a generalized increase in covalency over all M-L bonds. The more covalent tetrathiolate achieves a larger Deltaq(rlx) because the LMCT states responsible for relaxation are significantly lower in energy than those in the tetrachloride. The large observed electronic relaxation can make significant contributions to the thermodynamics and kinetics of electron transfer in inorganic systems.

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Section: Results and Analysissupporting

confidence: 86%

Electronic Structure Contributions to Electron-Transfer Reactivity in Iron−Sulfur Active Sites: 1. Photoelectron Spectroscopic Determination of Electronic Relaxation

Kennepohl

Solomon

2003

Inorg. Chem.

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“…The shape of the Fe L 2,3 XAS for chalcopyrite resembles that of KFeS 2 (Fig. 3b) which is high-spin Fe 3+ in a tetrahedral site (10Dq = 0.5 eV) (Atanasov et al, 1995). With an increasing crystal field, the weaker transition at the higher energy side of the L 3 structure disappears, while a low-energy shoulder grows in intensity, as is visible in hematite (Fe 2 O 3 , Fig.…”

Section: Fe L 23 Xasmentioning

confidence: 87%

“…The XAS L-edge spectra provided here (Figs. 2 and 3) were collected at the Synchrotron Radiation Source at CCLRC, Daresbury Laboratory, apart from the potassium thioferrite spectrum which is from Atanasov et al (1995). The Cu L 2,3 -edge spectra were obtained on experimental station 3.4, and the Fe L 2,3 -edge spectra on stations 1.1 and 5U.…”

Section: Data Collectionmentioning

confidence: 99%

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Copper oxidation state in chalcopyrite: Mixed Cu d9 and d10 characteristics

Pearce

Pattrick

Vaughan

et al. 2006

Geochimica et Cosmochimica Acta

150

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“…In the localized electron picture, the electron-hole asymmetry is well accounted for by assuming that the holes are doped not into the Fe 3d orbitals but into the ligand S 3p orbitals in the hole-doped system; this likely happens because the Fe 3+ ions are high-valence in the chalcogenides and belong to the negative chargetransfer regimes. 31 The antiferromagnetic interaction between Fe 3d electron spins and S 3p hole spin is considered to produce an effective ferromagnetic interaction between two Fe spins locating adjacent to each other across S site, which competes with the antiferromagnetic superexchange interaction between two adjacent Fe spins. This magnetic frustration breaks the antiferromagnetic ordering rapidly.…”

Section: The Effect Of Substitutionmentioning

confidence: 99%

Effects of stoichiometry and substitution in quasi-one-dimensional iron chalcogenideBaFe2S3

et al. 2015

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The effects of off-stoichiometry and elemental substitution on electronic properties of iron-based ladder compound BaFe2S3 are investigated. Resistivity and magnetization are revealed to be quite sensitive to the stoichiometry of Fe atoms, and 10 % deficiency at Fe sites reduces the antiferromagnetic transition temperature by 40 K. The antiferromagnetic transition temperature decreases even faster and collapse to zero with hole doping through 10 % K substitution at Ba site, while the antiferromagnetic ordering phase remains with electron doping through 20 % Co substitution at Fe site. Such electron-hole asymmetry is opposite to two-dimensional iron-based superconductors, and can be explained on the basis of both itinerant and localized electronic pictures.

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Electronic structure of tetrahedral iron(III)—sulfur clusters in alkaline thioferrates: an X-ray absorption study

Cited by 15 publications

References 34 publications

Electronic Structure Contributions to Electron-Transfer Reactivity in Iron−Sulfur Active Sites: 1. Photoelectron Spectroscopic Determination of Electronic Relaxation

Electronic Structure Contributions to Electron-Transfer Reactivity in Iron−Sulfur Active Sites: 1. Photoelectron Spectroscopic Determination of Electronic Relaxation

Copper oxidation state in chalcopyrite: Mixed Cu d9 and d10 characteristics

Effects of stoichiometry and substitution in quasi-one-dimensional iron chalcogenideBaFe2S3

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