Sulfur-Metal Orbital Hybridization in Sulfur-Bearing Compounds Studied by X-ray Emission Spectroscopy

Alonso-Mori, Roberto; Paris, Eleonora; Giuli, Gabriele; Eeckhout, S. G.; Kavčič, M.; Žitnik, M.; Bučar, K.; Pettersson, Lars G. M.; Glatzel, Pieter

doi:10.1021/ic100304z

Cited by 64 publications

(73 citation statements)

References 39 publications

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“…The intensity ratio of Kβ'/Kβ 1,3 varies depending on the binding form of S and can be used for speciation analysis [31][32][33][34]. At the Kα-line a small energy shift in dependence of the binding form can be observed when spectrometers with an extremely good angle resolution are used [35].…”

Section: Xrf-analysismentioning

confidence: 99%

Studies on the influence of H 2 S and SO 2 on the activity of a PdO/Al 2 O 3 catalyst for removal of oxygen by total oxidation of (bio-)methane at very low O 2 :CH 4 ratios

Ortloff

Bohnau

Kramar

et al. 2016

Applied Catalysis B: Environmental

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This work focuses on the deactivation and in-situ regeneration effects of a commercial PdO/Al 2 O 3 catalyst for removal of oxygen by oxidation of CH 4 at low O 2 :CH 4 ratios when hydrogen sulfide and sulfur dioxide are applied. The experimental work is carried out at an operating temperature range of 200 °C < T < 300 °C, atmospheric pressures and H 2 S contents of < 50 ppmv. SO 2 and H 2 S show a different behavior in the examined range of operating conditions. Due to the low operating temperatures and low oxygen contents applied in this work, it was possible to identify an intermediate species, presumably PdSO 3 , with an increased activity for the oxidation of methane. This stands in contrast to the literature, where SO 2 typically causes catalyst deactivation. Based on the experimental results, a reaction scheme was derived and kinetic measurements for each of the participating reactions were carried out separately.

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Section: Xrf-analysismentioning

confidence: 99%

Studies on the influence of H 2 S and SO 2 on the activity of a PdO/Al 2 O 3 catalyst for removal of oxygen by total oxidation of (bio-)methane at very low O 2 :CH 4 ratios

Ortloff

Bohnau

Kramar

et al. 2016

Applied Catalysis B: Environmental

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“…This and closely related approaches have been used to study the XES of a wide range of systems. [45][46][47][48] Equation (1.2) shows the oscillator strength computed within the dipole approximation; for heavy nuclei it has been observed that the quadrupole contribution to the transition moment can be significant. 49 Simulating XES directly from the Kohn-Sham calculation is computationally less expensive than TDDFT, since the additional TDDFT calculation is not required and the spectra for all core orbitals can be obtained from the same calculation.…”

Section: Introductionmentioning

confidence: 99%

Kohn-Sham density functional theory calculations of non-resonant and resonant x-ray emission spectroscopy

Hanson‐Heine

George

Besley

2017

The Journal of Chemical Physics

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The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm The accuracy of non-resonant and resonant (resonant inelastic X-ray scattering) X-ray emission spectra simulated based upon Kohn-Sham density functional theory is assessed. Accurate non-resonant X-ray emission spectra with the correct energy scale are obtained when short-range corrected exchangecorrelation functionals designed for the calculation of X-ray absorption spectroscopy are used. It is shown that this approach can be extended to simulate resonant inelastic X-ray scattering by using a reference determinant that describes a core-excited state. For this spectroscopy, it is found that a standard hybrid functional, B3LYP, gives accurate spectra that reproduce the features observed in experiment. However, the ability to correctly describe subtle changes in the spectra arising from different intermediate states is more challenging and requires averaging over conformations from a molecular dynamics simulation. Overall, it is demonstrated that accurate non-resonant and resonant X-ray emission spectra can be simulated directly from Kohn-Sham density functional theory.

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“…X-ray Emission Spectroscopy (XES) and Resonant Inelastic X-ray Scattering (RIXS) are very powerful in elucidating the electronic structure, providing information on the electron energies, local geometry, spin and valence state, etc. [9,17,18,19,20,21,22,23]. These tools can thus deliver complementary information to the usually employed ultrafast laser spectroscopies, when implemented in a pump-probe experiment with a laser pump and a time-delayed X-ray probe pulse.…”

Section: Introductionmentioning

confidence: 99%

Spin-state studies with XES and RIXS: From static to ultrafast

Vankó

Bordage

Glatzel

et al. 2013

Journal of Electron Spectroscopy and Related Phenomena

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We report on extending hard X-ray emission spectroscopy (XES) together with resonant inelastic X-ray scattering (RIXS) to study ultrafast phenomena in a pump-probe scheme at MHz repetition rates. The investigated system consists of low-spin (LS) Fe II complex compounds, where optical pulses induce a spinstate transition to their ≈ nanosecond-lived high-spin (HS) state. Time-resolved XES clearly reflects the spinstate variations with very high signal-to-noise ratio, in agreement with HS-LS difference spectra measured via thermally induced spin crossover, and reference HS-LS systems in static experiments. 1s2p RIXS, measured at the Fe 1s pre-edge region shows variations after laser excitation, which are consistent with the formation of the HS state. Our results demonstrate that now X-ray spectroscopy experiments with overall rather weak signals, such as RIXS, can be reliably exploited to study chemical and physical transformations on ultrafast time scales.

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Sulfur-Metal Orbital Hybridization in Sulfur-Bearing Compounds Studied by X-ray Emission Spectroscopy

Cited by 64 publications

References 39 publications

Studies on the influence of H 2 S and SO 2 on the activity of a PdO/Al 2 O 3 catalyst for removal of oxygen by total oxidation of (bio-)methane at very low O 2 :CH 4 ratios

Studies on the influence of H 2 S and SO 2 on the activity of a PdO/Al 2 O 3 catalyst for removal of oxygen by total oxidation of (bio-)methane at very low O 2 :CH 4 ratios

Kohn-Sham density functional theory calculations of non-resonant and resonant x-ray emission spectroscopy

Spin-state studies with XES and RIXS: From static to ultrafast

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