Evidence of the Anomalous Fluctuating Magnetic State by Pressure-Driven 4f Valence Change in EuNiGe3.

In rare-earth compounds with valence fluctuation, the proximity of the 4f level to the Fermi energy leads to instabilities of the charge configuration and the magnetic moment. Here, we provide direct experimental evidence for an induced magnetic polarization of the Eu3+ atomic shell with J = 0, due to intra-atomic exchange and spin-orbital coupling interactions with the Eu2+ atomic shell. By applying external pressure, a transition from antiferromagnetic to a fluctuating behavior in EuNiGe3 single crystals is probed. Magnetic polarization is observed for both valence states of Eu2+ and Eu3+ across the entire pressure range. The anomalous magnetism is discussed in terms of a homogeneous intermediate valence state where frustrated Dzyaloshinskii-Moriya couplings are enhanced by the onset of spin-orbital interaction and engender a chiral spin-liquid-like precursor.

Short-range order of compressed amorphous GeSe2.

The structure of amorphous GeSe2 (a-GeSe2) has been studied by means of a combination of two-edges X-ray absorption spectroscopy (XAS) and angle-dispersive X-ray diffraction under pressures up to about 30 GPa. Multiple-edge XAS data-analysis of a-GeSe2 at ambient conditions allowed us to reconstruct and compare the first-neighbor distribution function with previous results obtained by neutron diffraction with isotopic substitution. GeSe2 is found to remain amorphous up to the highest pressures attained, and a reversible 1.5 eV red-shift of the Ge K-edge energy indicating metallization, occurs between 10 GPa and 15 GPa. Two compression stages are identified by XAS structure refinement. First, a decrease of the first-neighbor distances up to about 10 GPa, in the same pressure region of a previously observed breakdown of the intermediate-range order. Second, an increase of the Ge-Se distances, bond disorder, and of the coordination number. This stage is related to a reversible non-isostructural transition involving a gradual conversion from tetra- to octa-hedral geometry which is not yet fully completed at 30 GPa.

Iron under pressure: "Kohn tweezers" and remnant magnetism.

In this work we investigate the magnetic and structural properties of bulk Fe and Fe nanoparticles under pressure with x-ray absorption and emission spectroscopies providing answers to two fundamental questions: (a) the chicken-or-egg problem for the magnetic and structural transitions and (b) magnetism in the high pressure hcp phase. The two transitions, inextricably linked in the bulk, are clearly decoupled in the nanoparticles, with the magnetic collapse preceding the structural transition. Ultrafast x-ray emission spectroscopy detects remnant magnetism, probably antiferromagnetic fluctuations, up to pressures of about 40 GPa in the hcp phase. This could be of direct relevance to the superconductivity in ϵ-Fe [K. Shimizu et al., Nature (London) 412, 316 (2001)] through the existence of a quantum critical point and associated magnetic fluctuations.

Pressure-induced valence crossover in superconducting CeCu2Si2.

Measurement of the Ce valence in the heavy fermion CeCu(2)Si(2) is reported for the first time under pressure and at low temperature (T=14 K) in proximity of the superconducting region. CeCu(2)Si(2) is considered as a strong candidate for a new type of pairing mechanism related to critical valence fluctuations which could set in at high pressure in the vicinity of the second superconducting dome. A quantitative estimate of the valence in this pressure region was achieved from the measurements of the Ce L(3) edge in the high-resolution partial-fluorescence yield mode and subsequent analysis of the spectra within the Anderson impurity model. While a clear increase of the Ce valence is found, the weak electron transfer and the continuous valence change under pressure suggests a crossover regime with the hypothetical valence line terminating at a critical end point T(cr) close to zero.

Inequivalent routes across the Mott transition in V2O3 explored by X-ray absorption.

The changes in the electronic structure of V2O3 across the metal-insulator transition induced by temperature, doping, and pressure are identified using high resolution x-ray absorption spectroscopy at the V pre-K edge. Contrary to what has been taken for granted so far, the metallic phase reached under pressure is shown to differ from the one obtained by changing doping or temperature. Using a novel computational scheme, we relate this effect to the role and occupancy of the a{1g} orbitals. This finding unveils the inequivalence of different routes across the Mott transition in V2O3.

Temperature dependence of the pre-edge structure in the Ti K-edge x-ray absorption spectrum of rutile.

The temperature dependence of the pre-edge features in x-ray absorption spectroscopy is reviewed. Then, the temperature dependence of the pre-edge structure at the K-edge of titanium in rutile TiO(2) is measured at low and room temperature. The first two peaks grow with temperature. The fact that these two peaks also correspond to electric quadrupole transitions is explained by a recently proposed theory.

Magnetic and crystallographic characterization of Pt(3)Mn(x)Cr(1-x) by XMCD and x-ray diffraction.

We have performed XMCD and diffraction measurements on the Pt(3)Mn(x)Cr(1-x) alloy, which show that the magnetization of Pt is independently influenced by the Mn or Cr 3d orbital. We find that the magnetic moment on Pt, and its decomposition into spin and orbital components, is uniquely determined by the relative number of Mn and Cr neighbors. We then investigate the effect of pressure on the magnetization of Pt in the Pt(3)Mn(0.5)Cr(0.5) alloy. Our high pressure data enable us to conclude that at 14 GPa the spin and orbital polarization of the Pt 5d band are augmented by about 70%, with no interaction between them.

Magnetic instabilities in Fe3C cementite particles observed with Fe K-edge x-ray circular dichroism under pressure.

The ferromagnetic interstitial iron compound Fe(3)C (cementite) is expected to have Invar properties, whereby a high-moment to low-moment transition should occur when the atomic volume is reduced below a critical value. We, therefore, examine the pressure dependence of the Fe K-edge x-ray magnetic circular dichroism in Fe(3)C at ambient temperature and pressures up to 20 GPa. We find clear evidence for a high-moment to low-moment transition around 10 GPa.

XMCD under pressure at the Fe K edge on the energy-dispersive beamline of the ESRF.

The present paper demonstrates the feasibility of X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) at high pressure at the Fe K edge on the ID24 energy-dispersive beamline of the ESRF. In 3d transition metals, performing experiments at the hard X-ray K edge rather than at the magnetically interesting soft X-ray L edges represents the only way to access the high-pressure regime obtainable with diamond anvil cells. The simultaneous availability of a local structure (XAS) and of a magnetic (XMCD) probe on the sample under identical thermodynamical conditions is essential for studying correlations between local structural and magnetic properties. The state-of-the-art theoretical understanding of K-edge XMCD data is briefly summarized, and the set-up of beamline ID24 for high-pressure XMCD experiments is illustrated and the conditions required to perform measurements at the K edges of 3d transition metals are underlined. Finally, two examples of recent high-pressure results at the Fe K edge in pure Fe and Fe3O4 powder are presented.

Dynamics of the magnetic and structural alpha-epsilon phase transition in iron.

We have studied the high-pressure iron bcc to hcp phase transition by simultaneous x-ray magnetic circular dichroism and x-ray absorption spectroscopy with an x-ray energy dispersive spectrometer. The combination of the two techniques allows us to obtain simultaneously information on both the structure and the magnetic state of iron under pressure. The magnetic and structural transitions simultaneously observed are sharp. Both are of first order in agreement with the theoretical prediction. The pressure domain of the transition observed (2.4+/-0.2 GPa) is narrower than that usually cited in the literature (8 GPa). Our data indicate that the magnetic transition slightly precedes the structural one, suggesting that the origin of the instability of the bcc phase in iron with increasing pressure is to be attributed to the effect of pressure on magnetism as predicted by spin-polarized full-potential total energy calculations.

Photoinduced ferrimagnetic systems in Prussian blue analogues C(I)xCo4[Fe(CN)6]y (C(I) = alkali cation). 4. Characterization of the ferrimagnetism of the photoinduced metastable state in Rb1.8Co4[Fe(CN)6]3.3-13H2O by K edges X-ray magnetic circular dichroism.

In Part 2 of this work, the electronic and local structure of the photoinduced metastable magnetic state of the Prussian blue analogue Rb1.8Co4[Fe(CN)6]3.3-13H2O were characterized. To determine directly the relative orientation of the magnetic moments of Co(II) and Fe(III) ions in the metastable state, and the nature of the exchange interaction between them, we performed X-ray magnetic circular dichroism (XMCD) experiments at the cobalt and iron K edges. We present the first direct experimental evidence of the antiferromagnetic interaction between the cobalt and the iron ions, leading to the ferrimagnetism of the photoinduced metastable state.

Nanosecond-resolved XMCD on ID24 at the ESRF to investigate the element-selective dynamics of magnetization switching of Gd-Co amorphous thin film.

The one-bunch filling mode of the ESRF is combined with a microcoil to generate a pulsed-magnetic-field pump phased with respect to the probe that is given by the bunch of photons emitted each turn (357 kHz). Nanosecond-resolved X-ray magnetic circular dichroism (XMCD) is carried out. Besides the microcoil, the two other key-elements are the energy-dispersive XAS spectrometer, which yields parallel data acquisition, and the diamond-based quarter-wave plate, which tunes the helicity of the photon alternatively left and right.

Two recent developments in XMCD.

This paper reports on two new technical developments concerning sample environments for X-ray magnetic circular dichroism (XMCD). The first measurements under high pressures of up to 30 GPa are described. The difficulties of combining the techniques of high pressure and XMCD are commented on. The second development involves the use of a fast-switching magnetic field. A new superconducting device is used to perform XMCD measurements on paramagnetic compounds in magnetic fields of up to 6 T. The small amplitude of the XMCD signal imposes, for a given signal-to-noise ratio, a noise less than a few 10(-5). The signal-to-noise ratio is improved by the use of a series of acquisitions, switching the magnetic field between each acquisition. A very fast switching mechanism has been built based on mechanical rotation of a superconducting coil, with the sample kept in place inside the coil. The XMCD signals at the L(II,III)-edges of paramagnetic rare-earth compounds have been measured at 4.5 K in fields of up to 6 T with a switching time of 11 s.

Quarter-wave plates and X-ray magnetic circular dichroism on ID24 at the ESRF.

The first XMCD measurements carried out on the ID24 energy-dispersive XAS beamline at the ESRF are reported. Circular-polarized X-rays are obtained using perfect diamond crystals as quarter-wave plates. The very small source divergence allows circular polarizations close to unity to be obtained.