Metal Kβ X-ray emission spectra of first row transition metal compounds

Gamblin, Stuart D.; Urch, D. S.

doi:10.1016/s0368-2048(00)00416-3

Cited by 81 publications

(81 citation statements)

References 25 publications

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“…This can be used either to determine the oxidation state of a system where the spin state (high spin vs. low spin) is known, or vice versa (Vankó et al 2006). In particular, the shift of the Kb 1,3 peak has been used to characterize small changes in oxidation state, where it was found that, compared to XANES, the shifts are more linearly correlated with the oxidation state and depend less on structure (Pizarro et al 2004;Visser et al 2001;Gamblin and Urch 2001).…”

Section: The Sensitivity Of Xesmentioning

confidence: 97%

X-ray emission spectroscopy

Bergmann

Glatzel²

2009

Photosynth Res

227

187

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We describe the chemical information that can be obtained by means of hard X-ray emission spectroscopy (XES). XES is presented as a technique that is complementary to X-ray absorption spectroscopy (XAS) and that provides valuable information with respect to the electronic structure (local charge- and spin-density) as well as the ligand environment of a 3d transition metal. We address non-resonant and resonant XES and present results that were recorded on Mn model systems and the Mn(4)Ca-cluster in the oxygen evolving complex of photosystem II. A brief description of the instrumentation is given with an outlook toward future developments.

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Section: The Sensitivity Of Xesmentioning

confidence: 97%

X-ray emission spectroscopy

Bergmann

Glatzel²

2009

Photosynth Res

227

187

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“…For a phenomenological description, the Kβ spectra can usually be fitted reasonably with three Voigt functions. 50 This might even serve as a useful approach for examining trends over a large set of compounds, for example; nevertheless, it has little use in quantifying the spin state for a transition which is not completely known. A more effective approach is to use the combination of proper reference spectra of known spin states of transition metals with similar local structure to model the spectral shape, or eventually to fit it to the data.…”

Section: B Line Shape Analysismentioning

confidence: 99%

Temperature- and pressure-induced spin-state transitions inLaCoO3

et al. 2006

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We report the continuous variation of the spin moment of cobalt in LaCoO3 across its temperature and pressure-induced spin transitions evidenced with Kβ emission spectra. The first thermal transition is best described by a transition to an orbitally nondegenerate intermediate spin (S=1) state. In parallel, continuous redistribution of the 3d electrons is also indicated by partial fluorescence yield X-ray absorption spectra. At high pressure, our study confirms that the material becomes low spin between 40 and 70 kbar at room temperature.

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“…This structure is known as the Kβ x line, and arises from a final state where an electron in the 3d valence band flips its spin [19]. The energy difference between the Kβ′satellite and the main Kβ 1,3 line, ΔE′has been shown to be a reliable parameter for spectral analysis [15,21]. XES spectra are normalized by their area and then aligned with the main peak of the G0 spectrum [22,23].…”

Section: Resultsmentioning

confidence: 99%

Hole doping and pressure effects on the II-II-V-based diluted magnetic semiconductor (Ba1−xKx)

et al. 2017

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We investigate doping-and pressure-induced changes in the electronic state of Mn 3d and As 4p orbitals in II-II-V based diluted magnetic semiconductor (Ba 1-x ,K x )(Zn 1-y ,Mn y ) 2 As 2 to shed light into the mechanism of indirect exchange interactions leading to high ferromagnetic ordering temperature (Tc = 230 K in optimally doped samples). A suite of x-ray spectroscopy experiments (emission, absorption and dichroism) show that the emergence, and further enhancement of ferromagnetic interactions with increased hole doping into the As 4p band is accompanied by a decrease in local 3d spin density at Mn sites. This is a result of increasing Mn 3d -As 4p hybridization with hole doping which enhances indirect exchange interactions between Mn dopants and gives rise to induced magnetic polarization in As 4p states. On the contrary, application of pressure suppresses exchange interactions. While Mn Kβ emission spectra show a weak response of 3d state to pressure, clear As 4p band broadening (hole delocalization) is observed under pressure ultimately leading to loss of ferromagnetism concomitant with a semiconductor to metal transition. The pressure response of As 4p and Mn 3d states is intimately connected with the evolution of the As-As interlayer distance and the geometry of the MnAs 4 tetrahedral units, which we probed with X-ray diffraction. Our results indicate that hole doping increases the degree of covalency between the anion (As) p states and cation (Mn) d states in the MnAs 4 tetrahedron, a crucial ingredient to promote indirect exchange interactions between Mn dopants and high Tc ferromagnetism. The instability of ferromagnetism and semiconducting state against pressure is mainly dictated by delocalization of anion p states. IntroductionSince the discovery of carrier-mediated ferromagnetism in Mn-doped InAs and GaAs compounds, diluted magnetic semiconductors (DMS) have received extensive attention due to their potential for manipulation of electron spin as a foundation of semiconductor spintronics [1][2][3][4][5]. Much progress has been made in the control of the exchange interactions, in which the magnetic phase can be turned on and off by applying electric field, light irradiation, or external pressure [6]. However, a microscopic understanding of the physical properties of DMS is still limited, e.g., the mechanism leading to magnetic ordering of dopants remains strongly debated [5,7]. Similarly, applications of high-Tc DMS in devices are yet to be realized. In the Mn-doped III-V semiconductors, substitution of trivalent cation Ga for Mn simultaneously introduces an acceptor and a source of magnetic moments. This dual role of Mn complicates theoretical understanding. Recently, Mn-doped II-II-V based semiconductor Ba(Zn,Mn) 2 As 2 was shown to become a high Tc

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Metal Kβ X-ray emission spectra of first row transition metal compounds

Cited by 81 publications

References 25 publications

X-ray emission spectroscopy

X-ray emission spectroscopy

Temperature- and pressure-induced spin-state transitions inLaCoO3

Hole doping and pressure effects on the II-II-V-based diluted magnetic semiconductor (Ba1−xKx)

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