Sulfur<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mi>K</mml:mi><mml:mi /><mml:mi>β</mml:mi></mml:math>x-ray emission spectra and electronic structures of some metal sulfides

Sugiura, Chikara; Gohshi, Yohichi; Suzuki, Isao

doi:10.1103/physrevb.10.338

Cited by 63 publications

(22 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The fluorescence energies as presented in Table are in good agreement with previously published data from the last 90 years (Figure ). All mean values with the only exception of S Kβ 1 for sulfite (Table ) are within the confidence intervals calculated from the previously published data .…”

Section: Resultssupporting

confidence: 90%

Distinction and quantification of inorganic sulfur species including thiosulfate by X‐ray fluorescence (WD‐XRF)

Hennings

Pleßow

2018

X-Ray Spectrometry

View full text Add to dashboard Cite

Sulfur occurs in a variety of inorganic and organic compounds with oxidation states from −II up to +VI. Differentiation of these species in solid geochemical samples can be challenging because of oxidation processes during sample preparation by acidic digestion. Applying pressed powder pellets and an analysis by wavelength‐dispersive X‐ray fluorescence minimises reactions with oxidants and water. Main subjects of this work were five inorganic sulfur species, sulfide −II, elemental sulfur 0, thiosulfate +II, sulfite +IV, and sulfate +VI, and the determination of their fluorescence energies in the sulfur X‐ray spectra. S Kα1,2 and S Kβ1 can be observed for all species, S Kβ′ satellites only for species with coordinated oxygen. The results are in good agreement with previously published data. Yet none of the 38 investigated papers from the past 90 years reported S Kα1,2 of thiosulfate, which was determined as E = 2,309.12 eV in this work apparently for the first time. Binary mixtures of sulfur species are strongly differing in their ability of being quantitatively differentiated, as a reliable quantification requires a sufficient difference of the respective fluorescence energies. Regression equations for each mixture can be used to calculate the ratio of mass fractions of the investigated species from the evaluated fluorescence energy. If boundary conditions are considered, the presented approaches can be applied for analyses of geochemical samples or quality control of technical products. The main advantage of the described methods is the option of implementation to everyday X‐ray fluorescence lab routine without substantial additional effort.

show abstract

Section: Resultssupporting

confidence: 90%

Distinction and quantification of inorganic sulfur species including thiosulfate by X‐ray fluorescence (WD‐XRF)

Hennings

Pleßow

2018

X-Ray Spectrometry

View full text Add to dashboard Cite

show abstract

“…S K~ XES have been reported for Cu2S by Domashevskaya et al (1976), Sugiura and Gohshi (1981), and for CuS by Nemnonov and Mikhailova (1974) and Sugiura et al (1974). Tossell (1978) presented MO/energy band calculations for CuS 7-, CuS 6-, CuSS-and CuS~-clusters, interpreted the XES and studied the electronic structures of CuS and Cu2S.…”

Section: Introductionmentioning

confidence: 87%

S K- and L-edge XANES and electronic structure of some copper sulfide minerals

Bancroft

Kasrai

et al. 1994

Phys Chem Minerals

View full text Add to dashboard Cite

Abstract. The S K-and L-edge x-ray absorption nearedge structures (XANES) of low bornite, cubanite, chalcocite, covellite, enargite and tetrahedrite have been measured with synchrotron radiation. The near-edge features are interpreted based on comparison with the S K-and L-edge spectra of chalcopyrite and a MO/energy band structure model. The XANES spectra of these sulfides reflect the DOS of unoccupied S s-, p-and d-like states near and above the Fermi level. In tetrahedral Cu-Fe sulfides, the Fe 3+ 3d crystal field band has much more significant DOS of unoccupied S 3p-and 3 s-like states than the Cu § 3d crystal field band. For Cu sulfides, the Cu § 3d crystal field band has the higher DOS of S 3p-and 3 s-like states in tetrahedral structure than in structures with the triangular CuS3 cluster. The shifts in both S K-and L-edges correlate approximately linearly with the energy gap.

show abstract

“…The S K-edge XANES of ZnS was first reported using a 50 cm bent quartz crystal spectrograph (Sugiura 1971;Sugiura et al 1974). Recently, the use of synchrotron radiation makes it possible to measure the XANES and EXAFS continuously over a large energy range above the threshold.…”

Section: Introductionmentioning

confidence: 99%

Sulfur K- and L-edge X-ray absorption spectroscopy of sphalerite, chalcopyrite and stannite

Bancroft

Kasrai

et al. 1994

Phys Chem Minerals

View full text Add to dashboard Cite

Abstract. Sulfur K-edge x-ray absorption spectra (XANES and EXAFS) and L-edge XANES of sphalerite (ZnS), chalcopyrite (CuFeS2) and stannite (Cu2FeSnS4) have been recorded using synchrotron radiation. The K-and L-edge XANES features are interpreted using a qualitative MO/energy band structure model. The densities of unoccupied states at the conduction bands of sphalerite, chalcopyrite and stannite are determined using S K-and L-edge XANES features (up to 15 eV above the edge), combined with published metal K-edge XANES. The S K-and L-edge XANES also indicate that, for sphalerite, the Fe 2 § 3 d band at the fundamental gap has little or no bonding hybridization with S 3p and S 3s orbitals; for chalcopyrite, the Cu § 3d and Fe 3+ 3d bands have strong mixing with S 3p and S 3s states, while for stannite the Cu § 3 d band strongly hybridizes with S 3 p and S 3 s orbitals, but the Fe 2 § 3 d band does not. The post-edge XANES features (15-50 eV above the edge) of sphalerite, chalcopyrite and stannite are similar. These features are related to the tetrahedral coordination of sulfur in all these structures, and interpreted by a multiple scattering model. The resonance energies from both the K-edge and L-edge XANES for these minerals are well correlated with reciprocal interatomic distances and lattice spaces. Sulfur K-edge EXAFS analyses using Fourier transform and curve fitting procedures are presented. Comparison of the structural parameters from EXAFS with x-ray structure data shows that the first shell bond distances (BD) from EXAFS are usually accurate to _+ 0.02/~, and that coordination numbers (CN) are generally accurate to + 20 percent. For sphalerite, EXAFS analysis yields the structure parameters for the first three neighbour shells around a sulfur atom; the BD and CN even for the third shell are in close agreement with the x-ray structure, and the Debye-Waller term decreases from the first shell to the third shell. It is shown that sphalerite (ZnS) is a good model compound for EXAFS analysis of sulfur in chalcogenide glasses and metalloproteins.

show abstract

SulfurKβx-ray emission spectra and electronic structures of some metal sulfides

Cited by 63 publications

References 34 publications

Distinction and quantification of inorganic sulfur species including thiosulfate by X‐ray fluorescence (WD‐XRF)

Distinction and quantification of inorganic sulfur species including thiosulfate by X‐ray fluorescence (WD‐XRF)

S K- and L-edge XANES and electronic structure of some copper sulfide minerals

Sulfur K- and L-edge X-ray absorption spectroscopy of sphalerite, chalcopyrite and stannite

Contact Info

Product

Resources

About