Resonant inelastic x-ray scattering of CeB6 at the Ce L1- and L3-edges

Abstract

We report a resonant inelastic x-ray scattering (RIXS) study of crystalline CeB(6). Ce L(α1,2) RIXS was measured with excitation energies resonant with the Ce L(3)-edge. A lifetime-broadening suppressed x-ray absorption near-edge structure (LBS-XANES), which successfully reproduced the L(α1,2) RIXS spectra over wide ranges of excitation and emission energies, was simulated using the SIM-RIXS program. A pre-edge structure in the LBS-XANES can be resolved, and many-body effects were suggested in the L(α1,2) RIXS around the Ce L(3)-edge energy. No convincing signs of Ce (II) or Ce (IV) states were observed in the LBS-XANES. Ce L(γ4) RIXS was measured at 302 K and 28 K with excitation energies across the Ce L(1)-edge. The interactions of p-valence electrons between Ce and B(6) were found to be considerably small, regardless of temperature. Thus, the electronic state of CeB(6) was concluded to be suitably described as a nominally Ce(4f(1))(3+)(e(-))(B(6))(2-) system with some hybridization among all valence orbitals of Ce and B.

A new method for determining the valence of lanthanide compounds: Lγ4 emission spectroscopy

“…In addition, even the inherent resolution limitation owing to the lifetime-broadening can be somewhat overcome by using partial uorescence yield (PFY) detection [15][16][17][18] or resonant inelastic X-ray scattering (RIXS) detection. 19 However, in XANES and its related methods, the uncertainties accompanying the estimation of the continuum states cannot be disregarded. 17,18 In fact, from a similar experimental L III XANES of SmB 6 at room temperature, Beaurepaire et al 12 and Mizumaki et al 14 have derived somewhat different valence values of 2.63 and 2.59 AE 0.01, respectively.…”

Chemical effects of high‐resolution YbLγ4 emission spectra: a possible probe for chemical analysis

“…The Yb Lγ 4 spectra clearly exhibit double‐peak structures, which were not observed in the Lγ 4 spectra of I–Nd . For the Lγ 4 spectra of Sm and Eu, a hump structure that is dependent on the valence states was reported and attributed mainly to 4f5p exchange interactions.…”

“…Despite the rather extensive studies of the chemical effects on lighter elements, very little information is available regarding heavier elements, including lanthanides . Very recently, we reported the relatively large chemical effects of the Lγ 4 ( L I O II,III ) emissions of lanthanides . The Lγ 4 emissions of the middle lanthanides Sm and Eu show valence‐dependent chemical shifts of 4–5 eV, whereas that of the early lanthanide Ce exhibits ligand‐dependent profile changes.…”

“…Very recently, we reported the relatively large chemical effects of the Lγ 4 ( L I O II,III ) emissions of lanthanides . The Lγ 4 emissions of the middle lanthanides Sm and Eu show valence‐dependent chemical shifts of 4–5 eV, whereas that of the early lanthanide Ce exhibits ligand‐dependent profile changes. The present report describes chemical effects on the Lγ 4 emission of a late lanthanide and the last element in the f‐block, Yb ( Z = 70).…”

Pressure dependence of Ce valence in CeRhIn5

“…[16,18] The pre-edge feature likely corresponds to the 2p  4f quadrupole transition, as discussed in several resonant inelastic xray scattering (RIXS) and XANES measurements performed on other lanthanide compounds. [29][30][31][32] The predicted change in Ce valence should be observed by a peak developing in the f 0 region above the critical pressure. At T=300 K, the f 1 peak decreases in amplitude with pressure, but the f 0 region remains unaffected.…”