The valence state of Yb ions in beta-YbAlB4 and its polymorph alpha-YbAlB4 has been investigated by using X-ray absorption and emission spectroscopy in SPring-8 at temperatures from 2 to 280 K. The observed Yb valence is 2.78 +- 0.01 in beta-YbAlB4 at 2 K by using the X-ray emission spectroscopy. The valence is found to gradually increase with increasing temperature toward the trivalent state, and the characteristic temperature of the valence fluctuation is expected to be about 290 K. We also found a small increase in the Yb valence (~0.002) by applying a magnetic field of 32 T at 40 K to beta-YbAlB4.
In order to probe the changes in the valence state and magnetic properties of Eu metal under extreme pressure, x-ray absorption near-edge spectroscopy, x-ray magnetic circular dichroism and synchrotron Mossbauer spectroscopy experiments have been carried out. The Mossbauer isomer shift exhibits an anomalous pressure dependence, passing through a maximum near 20 GPa. Density functional theory has been applied to give insight into the pressure-induced changes in both Eus electronic structure and Mossbauer isomer shift. Contrary to previous reports, Eu is found to remain nearly divalent to the highest pressures reached (87 GPa) with magnetic order persisting to at least 50 GPa. These results should lead to a better understanding of the nature of the superconducting state found above 75 GPa and of the sequence of structural phase transitions observed to 92 GPa.
X-ray magnetic circular dichroism (XMCD) at the Eu L-edge (2p->5d) in two compounds exhibiting valence fluctuation, namely EuNi2(Si0.18Ge0.82)2 and EuNi2P2, has been investigated at pulsed high magnetic fields of up to 40 T. A distinct XMCD peak corresponding to the trivalent state (Eu3+; f6), whose ground state is nonmagnetic (J=0), was observed in addition to the main XMCD peak corresponding to the magnetic (J=7/2) divalent state (Eu2+; f7). This result indicates that the 5d electrons belonging to both valence states are magnetically polarized. It was also found that the ratio P5d(3+)/P5d(2+) between the polarization of 5d electrons (P5d) in the Eu3+ state and that of Eu2+ is ~ 0.1 in EuNi2(Si0.18Ge0.82)2 and ~ 0.3 in EuNi2P2 at magnetic fields where their macroscopic magnetization values are the same. The possible origin of the XMCD of the Eu3+ state and an explanation of the dependence of P5d(3+)/P5d(2+) on the material are discussed in terms of hybridization between the conduction electrons and the f electrons.
Electronic structures of the quantum critical superconductor beta-YbAlB4 and its polymorph alpha-YbAlB4 are investigated by using bulk-sensitive hard x-ray photoemission spectroscopy. From the Yb 3d core level spectra, the values of the Yb valence are estimated to be ~2.73 and ~2.75 for alpha- and beta-YbAlB4, respectively, thus providing clear evidence for valence fluctuations. The valence band spectra of these compounds also show Yb2+ peaks at the Fermi level. These observations establish an unambiguous case of a strong mixed valence at quantum criticality for the first time among heavy fermion systems, calling for a novel scheme for a quantum critical model beyond the conventional Doniach picture in beta-YbAlB4.
Fermi liquid theory, the standard theory of metals, has been challenged by a number of observations of anomalous metallic behavior found in the vicinity of a quantum phase transition. The breakdown of the Fermi liquid is accomplished by fine-tuning the material to a quantum critical point using a control parameter such as the magnetic field, pressure, or chemical composition. Our high precision magnetization measurements of the ultrapure f-electron based superconductor {beta}-YbAlB4 demonstrate a scaling of its free energy indicative of zero-field quantum criticality without tuning in a metal. The breakdown of Fermi-liquid behavior takes place in a mixed-valence state, in sharp contrast with other known examples of quantum critical f-electron systems that are magnetic Kondo lattice systems with integral valence.
We report the first high-field x-ray diffraction experiment using synchrotron x-rays and pulsed magnetic fields exceeding 30 T. Lattice deformation due to a magnetic-field-induced valence transition in YbInCu4 is studied. It has been found that the Bragg reflection profile at 32 K changes significantly at around 27 T due to the structural transition. In the vicinity of the transition field the low-field and the high-field phases are observed simultaneously as the two distinct Bragg reflection peaks: This is a direct evidence of the fact that the field-induced valence state transition is the first order phase transition. The field-dependence of the low-field-phase Bragg peak intensity is found to be scaled with the magnetization.
Y. H. Matsuda
,T. Nakamura
,K. Kuga
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(2013)
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"Synchrotron X-ray Spectroscopy Study on the Valence State in alpha- and beta-YbAlB4 at Low Temperatures and High Magnetic Fields"
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Yasuhiro Matsuda
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