Chemical dependence of interatomic X-ray transition energies and intensities – a study of Mn Kβ″ and Kβ2,5 spectra

Bergmann, Uwe; Horne, Craig R.; Collins, Terrence J.; Workman, José M.; Cramer, Stephen P.

doi:10.1016/s0009-2614(99)00095-0

Cited by 168 publications

(222 citation statements)

References 25 publications

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“…These features, also known as ''crossover'' peaks, have been assigned as ligand 2s→ metal 1s transitions, and they reflect the ligand 2s binding energies. 18 However, the origin of the transition intensity is not completely settled.…”

Section: Resultsmentioning

confidence: 99%

Anisotropic valence→core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]⋅H2O single crystal: Experimental results and density functional calculations

Bergmann

Bendix

Glatzel

et al. 2002

The Journal of Chemical Physics

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High resolution x-ray fluorescence spectra have been recorded for emission in different directions from a single crystal of the compound ͓Rh͑en͒ 3 ͔͓Mn͑N͒͑CN͒ 5 ͔•H 2 O. The spectra are interpreted by comparison with density functional theory ͑DFT͒ electronic structure calculations. The K␤Љ line, which is strongly polarized along the Mn-N axis, can be viewed as an N(2s)→Mn(1s) transition, and the angular dependence is understood within the dipole approximation. The so-called K␤ 2,5 region has numerous contributions but is dominated by Mn(4p) and C(2s)→Mn(1s) transitions. Transition energy splittings are found in agreement with those of calculated occupied molecular orbitals to within 1 eV. Computed relative transition probabilities reproduce experimentally observed trends.

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Section: Resultsmentioning

confidence: 99%

Anisotropic valence→core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]⋅H2O single crystal: Experimental results and density functional calculations

Bergmann

Bendix

Glatzel

et al. 2002

The Journal of Chemical Physics

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“…17 High energy resolution XES enables to probe the ligand environment of a metal of interest. 12,[18][19][20][21][22] Access to the ligand orbital is obtained by ionizing the core electron and measuring the following valence-to-core transition. This decay channel involves the valence electrons of the ligands and therefore provides information about the highest occupied electronic levels in matter.…”

Section: Introductionmentioning

confidence: 99%

A von Hamos x-ray spectrometer based on a segmented-type diffraction crystal for single-shot x-ray emission spectroscopy and time-resolved resonant inelastic x-ray scattering studies

Szlachetko

Nachtegaal

Boni

et al. 2012

Review of Scientific Instruments

167

145

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We report on the design and performance of a wavelength-dispersive type spectrometer based on the von Hamos geometry. The spectrometer is equipped with a segmented-type crystal for x-ray diffraction and provides an energy resolution in the order of 0.25 eV and 1 eV over an energy range of 8000 eV-9600 eV. The use of a segmented crystal results in a simple and straightforward crystal preparation that allows to preserve the spectrometer resolution and spectrometer efficiency. Application of the spectrometer for time-resolved resonant inelastic x-ray scattering and single-shot x-ray emission spectroscopy is demonstrated.

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“…For example, nitrogen and oxygen ligands can be clearly distinguished. [5] Also, ligand protonation yields spectral changes that can be assigned to e.g. OH -or H 2 O groups ( Fig.…”

Section: Non-resonant Xesmentioning

confidence: 99%

“…Their intensities depend on the incident energy and it is thus possible to identify them in the Kβ satellite spectrum. [6] 2+ (left) and [Mn(H 2 O) 5 OH] + (right). Ligand deprotonation lowers the symmetry and yields an additional peak (S2) that can be assigned to a molecular orbital localized on the OH ligand.…”

Section: Non-resonant Xesmentioning

confidence: 99%

Hard X-Ray Photon-In-Photon-Out Spectroscopy with Lifetime Resolution — of XAS, XES, RIXSS and HERFD

Glatzel

Sikora

Eeckhout

et al. 2007

AIP Conference Proceedings

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Abstract. Spectroscopic techniques that aim to resolve the electronic configuration and local coordination of a central atom by detecting inner-shell radiative decays following photoexcitation using hard X-rays are presented. The experimental setup requires an X-ray spectrometer based on perfect crystal Bragg optics. The possibilities arising from non-resonant (X-Ray Emission Spectroscopy -XES) and resonant excitation (Resonant Inelastic X-Ray Scattering Spectroscopy -RIXSS, High-Energy-Resolution Fluorescence Detected (HERFD) XAS) are discussed when the instrumental energy broadenings of the primary (beamline) monochromator and the crystal spectrometer for x-ray emission detection are on the order of the core hole lifetimes of the intermediate and final electronic states. The small energy bandwidth in the emission detection yields line-sharpened absorption features. In transition metal compounds, electron-electron interactions as well as orbital splittings and fractional population can be revealed. Combination with EXAFS spectroscopy enables to extent the k-range beyond unwanted absorption edges in the sample that limit the EXAFS range in conventional absorption spectroscopy.

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Chemical dependence of interatomic X-ray transition energies and intensities – a study of Mn Kβ″ and Kβ2,5 spectra

Cited by 168 publications

References 25 publications

Anisotropic valence→core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]⋅H2O single crystal: Experimental results and density functional calculations

Anisotropic valence→core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]⋅H2O single crystal: Experimental results and density functional calculations

A von Hamos x-ray spectrometer based on a segmented-type diffraction crystal for single-shot x-ray emission spectroscopy and time-resolved resonant inelastic x-ray scattering studies

Hard X-Ray Photon-In-Photon-Out Spectroscopy with Lifetime Resolution — of XAS, XES, RIXSS and HERFD

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