Charge-transfer effect on the linewidth of Fe<i>K</i>α x-ray fluorescence spectra

Kawai, Jun; Suzuki, Chikashi; Adachi, Hirohiko; Konishi, Tokuzo; Gohshi, Yohichi

doi:10.1103/physrevb.50.11347

Cited by 57 publications

(39 citation statements)

References 47 publications

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Section: Determination Of the Spin Momentum From Xesmentioning

confidence: 99%

“…13,19 In the case of KR, multiplet theory suggests that eq 1 concerns the width of the KR 1 line. 18,19,21 To our knowledge, this has not been exploited yet in following spin transitions, the plausible reason being the observed deviations from this expected behavior, for example, in HS compounds of transitional metals. 19,37 However, as it can be seen in Figure 6, for our model compounds, these line widths clearly correlate with the spin, which allows us to distinguish different spin states.…”

Section: Determination Of the Spin Momentum From Xesmentioning

confidence: 99%

“…It was found that the width of the KR 1 line depends on the spin state; 18 however, deviations from this behavior were also observed. 19 Nevertheless, a systematic theoretical work concluded that the KR spectra encompass spinpolarized information. 17 Therefore, it might be rewarding to inspect all XES features for spin sensitivity.…”

Section: Introductionmentioning

confidence: 99%

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Probing the 3d Spin Momentum with X-ray Emission Spectroscopy: The Case of Molecular-Spin Transitions

et al. 2006

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We report X-ray emission spectra of Fe III , Fe II , and Co II spin-crossover compounds in their high-spin and low-spin forms. It is shown that all X-ray emission features are sensitive to the spin state. Variations of the K and the KR emission line shapes, which are in agreement with theory, can be used as quantitative probes of the spin state; it is suggested that with appropriate reference experiments one can extract the spin momentum for a general case. Resonant X-ray emission spectra unveil details of the redistribution of electrons on the 3d levels associated with the spin-state change by revealing features at the X-ray absorption preedge not accessible through standard absorption measurements.

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Section: Determination Of the Spin Momentum From Xesmentioning

confidence: 99%

Section: Determination Of the Spin Momentum From Xesmentioning

confidence: 99%

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Probing the 3d Spin Momentum with X-ray Emission Spectroscopy: The Case of Molecular-Spin Transitions

et al. 2006

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“…Kawai et al analyzed the charge-transfer effect on the linewidth of Fe K␣ lines using a spinunrestricted DV-X␣ molecular-orbital calculation. 14 They calculated the effective number of unpaired electrons in the ground state and in the presence of a 1s hole and obtained similar numbers for the excited states of FeO and Fe 2 O 3 giving rise to almost identical K␣ fluorescence emission. Von dem Borne and collaborators performed 3p XPS mea-surements and calculations for atomic Mn including, among other configurations, 4s to 3d shake-down processes, which can be considered the atomic equivalent to ligand-to-metal charge transfer in solids and molecules.…”

Section: Introductionmentioning

confidence: 99%

Influence of the core hole onKβemission following photoionization or orbital electron capture: A comparison using MnO and55Fe2
Glatzel
¹
,
Bergmann
²
,
Groot
³

et al. 2001
Phys. Rev. B
52
1
34
0
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The Mn K␤ fluorescence emission in MnO after photoionization and in 55 Fe 2 O 3 after radioactive electron capture decay from the K shell have been measured using a crystal array spectrometer with an instrumental energy bandwidth of 0.7 eV ͑full width at half maximum͒. Both compounds have a 3d 5 valence electron configuration in the ionic approximation. It is found that the spectral features after K capture in 55 Fe 2 O 3 are shifted in emission energy and are sharper, compared to the spectra following photoionization in MnO, i.e., the spectra exhibit a dependence on the mode of excitation. Crystal-field multiplet calculations including ligandto-metal charge transfer have been carried out for the 1s intermediate states as well as for the 3p to 1s (K␤) radiative transition. The populated 1s intermediate states after photoionization are found to be spread over several eV. In comparison, only the lowest-lying 1s intermediate states split by the weak (1s,3d) exchange interaction are populated after K capture. It is proposed that the differences in population of the 1s intermediate states together with a term-dependent final-state lifetime broadening can account for the changes in the spectral shapes due to the different modes of excitation.

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“…1 Both the line width and the peak shift of the Kα1 line are strongly correlated with the number of unpaired 3d electrons, or valency, and the ligands in the transition metal compounds. 2,3 The profile changes of the high-resolution Kα Xray fluorescence spectra due to the chemical states and their theoretical interpretations were reported for Sc, 4 Ti, 5 V, 6 Cr, 7 Mn, 7 Fe, 8 Co, 9 and Cu. 10 For Ni, the chemical effects on the line shape in high-resolution Kα X-ray spectra were for only a few compounds, 2,3,[11][12][13][14][15] but along with the development of rechargeable electric batteries, the number of reported compounds became large.…”

Section: Introductionmentioning

confidence: 99%

Chemical Effects in High-Resolution Nickel Kα X-Ray Fluorescence Spectra

2005

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IntroductionThough X-ray fluorescence analysis is used for elemental analysis, high-resolution measurements with a double-crystal Xray fluorescence spectrometer reveal a chemical shift of the characteristic X-ray lines owing to a change of the chemical environment. 1 Both the line width and the peak shift of the Kα1 line are strongly correlated with the number of unpaired 3d electrons, or valency, and the ligands in the transition metal compounds. 2,3 The profile changes of the high-resolution Kα Xray fluorescence spectra due to the chemical states and their theoretical interpretations were reported for Sc, 4 Ti, 5 V, 6 Cr, 7 Mn, 7 Fe, 8 Co, 9 and Cu. 10 For Ni, the chemical effects on the line shape in high-resolution Kα X-ray spectra were for only a few compounds, 2,3,[11][12][13][14][15] but along with the development of rechargeable electric batteries, the number of reported compounds became large. 16 However, the interpretation of the line width has been different among researchers.Tsutsumi 17 proposed an interpretation that the line width was proportional to the multiplicity, J(2S + 1), of the 3d level, where J is the exchange integral. Then Kawai et al. 18 proposed a charge-transfer mechanism, where, in the 1s -1 hole state, ligand 2p electrons were attracted by some of the Ni atoms and consequently the 3d holes were filled by the electrons transferred from a ligand (well-screened state), while the other Ni atoms do not attract any electrons from the ligand (poorly screened state) because of a too fast atomic process. As a consequence of these two processes, the X-ray peak was split into two peaks due to the presence or absence of the chargetransfer from the ligand, and became broader. As mentioned above, quite similar papers 15,16 on Ni measured by doublecrystal spectrometers were published in the same issue of the journal, X-Ray Spectrometry, guest edited by one of the present authors. Konishi et al. 16 measured 32 nickel compounds, which were interpreted by Kawai's charge-transfer mechanism. 18 Shigemi et al. 15 measured two nickel compounds and a metal reference, which were interpreted by Tsutsumi's exchange splitting theory. 17 Because a paper that denies the editor's theory was published in the journal edited by the editor does not mean that the editor has accepted the denial. It is the duty of the journal editor to open the door for various ways of discussion. The line broadenings of late transition-metal compounds, such as nickel and cobalt, are not remarkable compared with those of early transition metal compounds. This is well interpreted in such a way that Kawai's charge-transfer mechanism plays a major role for late transition-metal compounds, while Tsutsumi's exchange mechanism plays a major role for early transition-metal compounds. 19 The purpose of the present paper is to show the reproducibility of Konishi's experiment in another type of spectrometer, as well as to prove the charge-transfer mechanism through a molecular orbital calculation. ExperimentalThe double-crystal spectrometers use...

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Charge-transfer effect on the linewidth of FeKα x-ray fluorescence spectra

Cited by 57 publications

References 47 publications

Probing the 3d Spin Momentum with X-ray Emission Spectroscopy: The Case of Molecular-Spin Transitions

Probing the 3d Spin Momentum with X-ray Emission Spectroscopy: The Case of Molecular-Spin Transitions

Influence of the core hole onKβemission following photoionization or orbital electron capture: A comparison using MnO and55Fe2
Glatzel
¹
,
Bergmann
²
,
Groot
³

et al. 2001
Phys. Rev. B
52
1
34
0
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Chemical Effects in High-Resolution Nickel Kα X-Ray Fluorescence Spectra

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Charge-transfer effect on the linewidth of FeKα x-ray fluorescence spectra

Cited by 57 publications

References 47 publications

Probing the 3d Spin Momentum with X-ray Emission Spectroscopy: The Case of Molecular-Spin Transitions

Probing the 3d Spin Momentum with X-ray Emission Spectroscopy: The Case of Molecular-Spin Transitions

Influence of the core hole onKβemission following photoionization or orbital electron capture: A comparison using MnO and55Fe2Glatzel1, Bergmann2, Groot3 et al. 2001Phys. Rev. B521340View full textAdd to dashboardCite

Chemical Effects in High-Resolution Nickel Kα X-Ray Fluorescence Spectra

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Influence of the core hole onKβemission following photoionization or orbital electron capture: A comparison using MnO and55Fe2
Glatzel
¹
,
Bergmann
²
,
Groot
³

et al. 2001
Phys. Rev. B
52
1
34
0
View full text Add to dashboard Cite