A. Al-Zein

CaIrO3: a spin-orbit Mott insulator beyond the j(eff) ground state.

In CaIrO3, electronic correlation, spin-orbit coupling, and tetragonal crystal field splitting are predicted to be of comparable strength. However, the nature of its ground state is still an object of debate, with contradictory experimental and theoretical results. We probe the ground state of CaIrO3 and assess the effective tetragonal crystal field splitting and spin-orbit coupling at play in this system by means of resonant inelastic x-ray scattering. We conclude that insulating CaIrO3 is not a j(eff) = 1/2 iridate and discuss the consequences of our finding to the interpretation of previous experiments. In particular, we clarify how the Mott insulating state in iridates can be readily extended beyond the j(eff) = 1/2 ground state.

Persistent Paramagnons Deep in the Metallic Phase of Sr_{2-x}La_{x}IrO_{4}.

We have studied the magnetic excitations of electron-doped Sr_{2-x}La_{x}IrO_{4} (0≤x≤0.10) using resonant inelastic x-ray scattering at the Ir L_{3} edge. The long-range magnetic order is rapidly lost with increasing x, but two-dimensional short-range order (SRO) and dispersive magnon excitations with nearly undiminished spectral weight persist well into the metallic part of the phase diagram. The magnons in the SRO phase are heavily damped and exhibit anisotropic softening. Their dispersions are well described by a pseudospin-1/2 Heisenberg model with exchange interactions whose spatial range increases with doping. We also find a doping-independent high-energy magnetic continuum, which is not described by this model. The spin-orbit excitons arising from the pseudospin-3/2 manifold of the Ir ions broaden substantially in the SRO phase, but remain largely separated from the low-energy magnons. Pseudospin-1/2 models are therefore a good starting point for the theoretical description of the low-energy magnetic dynamics of doped iridates.

CeRu4Sn6: a strongly correlated material with nontrivial topology.

Topological insulators form a novel state of matter that provides new opportunities to create unique quantum phenomena. While the materials used so far are based on semiconductors, recent theoretical studies predict that also strongly correlated systems can show non-trivial topological properties, thereby allowing even the emergence of surface phenomena that are not possible with topological band insulators. From a practical point of view, it is also expected that strong correlations will reduce the disturbing impact of defects or impurities, and at the same increase the Fermi velocities of the topological surface states. The challenge is now to discover such correlated materials. Here, using advanced x-ray spectroscopies in combination with band structure calculations, we infer that CeRu4Sn6 is a strongly correlated material with non-trivial topology.

High-Pressure Structural and Vibrational Study of PbZr0.40Ti0.60O3

The high-pressure structure and dynamics of PbZr0.40Ti0.60O3 were investigated by means of neutron diffraction, X-ray diffraction, and resonance Raman spectroscopy. The complex (P4mm, Cm, Cc, F1, F1) phase transition sequence is characterized by these techniques. On the basis of the results of structure refinements, the high-pressure behavior of the spontaneous polarization, the (Zr,Ti)O6 rotation angles, and the polarization rotation angle are obtained. Moreover, resonance Raman spectra combined with previous Raman data in the literature provide evidence that the pressure-induced transition to the monoclinic Cm space group and the above transition sequence terminating in a paraelectric state are general features of Pb(Zr(1-x)Ti(x))O3 (0.48 < or = x < or = 1).

Improving the energy resolution of bent crystal X-ray spectrometers with position-sensitive detectors

A new measurement technique for X-ray spectrometers equipped with a position-sensitive detector is introduced. It is based on the computational compensation of the effects of internal stress of curved analyser crystals to improve the energy resolution in the measurements of point-like samples with no loss of intensity.

Direct bulk-sensitive probe of 5f symmetry in URu2Si2

Significance The hidden order problem in URu2Si2 is an unanswered question in the field of strongly correlated electron materials. Although it has been studied for several decades, there is still no consensus about how this new phase forms. Understanding the hidden order phase formation is not only an intellectual problem, it will also advance concepts for designing quantum materials with new exotic properties. Many hidden order scenarios are based on the assumption of certain ground-state symmetries and the present study addresses this aspect. A spectroscopic technique, nonresonant inelastic X-ray scattering, that has become available through the use of high-brilliance synchrotrons, allows us to measure directly in a bulk-sensitive experiment the symmetry of the 5f ground-state wave function in URu2Si2. The second-order phase transition into a hidden order phase in URu2Si2 goes along with an order parameter that is still a mystery, despite 30 years of research. However, it is understood that the symmetry of the order parameter must be related to the symmetry of the low-lying local electronic f-states. Here, we present results of a spectroscopic technique, namely core-level nonresonant inelastic X-ray scattering (NIXS). This method allows for the measurement of local high-multipole excitations and is bulk-sensitive. The observed anisotropy of the scattering function unambiguously shows that the 5f ground-state wave function is composed mainly of the Γ1 with majority Jz = |4⟩ + |−4⟩ and/or Γ2 singlet states. The incomplete dichroism indicates the possibility that quantum states of other irreducible representation are mixed into the ground state.

In situ characterization of the decomposition behavior of Mg(BH4)2 by X-ray Raman scattering spectroscopy

We present an in situ study of the thermal decomposition of Mg(BH4)2 in a hydrogen atmosphere of up to 4 bar and up to 500 °C using X-ray Raman scattering spectroscopy at the boron K-edge and the magnesium L2,3-edges. The combination of the fingerprinting analysis of both edges yields detailed quantitative information on the reaction products during decomposition, an issue of crucial importance in determining whether Mg(BH4)2 can be used as a next-generation hydrogen storage material. This work reveals the formation of reaction intermediate(s) at 300 °C, accompanied by a significant hydrogen release without the occurrence of stable boron compounds such as amorphous boron or MgB12H12. At temperatures between 300 °C and 400 °C, further hydrogen release proceeds via the formation of higher boranes and crystalline MgH2. Above 400 °C, decomposition into the constituting elements takes place. Therefore, at moderate temperatures, Mg(BH4)2 is shown to be a promising high-density hydrogen storage material with great potential for reversible energy storage applications.

Crystal field splitting in Srn+1IrnO3n+1 (n = 1,2) iridates probed by x-ray Raman spectroscopy

Nonresonant Raman spectroscopy in the hard x-ray regime has been used to explore the electronic structure of the first two members of the Ruddlesden-Popper series Srn+1IrnO3n+1 of iridates. By tuning the photon energy transfer around 530 eV, we have been able to explore the oxygen K-near-edge structure with bulk sensitivity. The angular dependence of the spectra has been exploited to assign features in the 528–535 eV energy range to specific transitions involving the Ir 5d orbitals. This has allowed us to extract reliable values for both the t2g–eg splitting arising from the cubic component of the crystal field (10Dq), in addition to the splitting of the eg orbitals due to tetragonal distortions. The values we obtain are (3.8, 1.6) eV and (3.55, 1.9) eV for Sr2IrO4 and Sr3Ir2O7, respectively.

Evidence of quantum dimer excitations in Sr3Ir2O7

The magnetic excitation spectrum in the bilayer iridate Sr3Ir2O7 has been investigated using high-resolution resonant inelastic x-ray scattering (RIXS) performed at the iridium L-3 edge and theoretical techniques. A study of the systematic dependence of the RIXS spectrum on the orientation of the wave-vector transfer Q, with respect to the iridium-oxide bilayer, has revealed that the magnon dispersion is comprised of two branches well separated in energy and gapped across the entire Brillouin zone. Our results contrast with those of an earlier study which reported the existence of a single dominant branch. While these earlier results were interpreted as two overlapping modes within a spin-wave model of weakly coupled iridium-oxide planes, our results are more reminiscent of those expected for a system of weakly coupled dimers. In this latter approach, the lower-and higher-energy modes find a natural explanation as those corresponding to transverse and longitudinal fluctuations, respectively. We have therefore developed a bond-operator theory which describes the magnetic dispersion in Sr3Ir2O7 in terms of quantum dimer excitations. In our model, dimerization is produced by the leading Heisenberg exchange J(c), which couples iridium ions in adjacent planes of the bilayer. The Hamiltonian also includes in-plane exchange J, as well as further neighbor couplings and relevant anisotropies. The bond-operator theory provides an excellent account of the dispersion of both modes, while the measured Q dependence of the RIXS intensities is in reasonable qualitative accord with the spin-spin correlation function calculated from the theory. We discuss our results in the context of the quantum criticality of bilayer dimer systems in the presence of anisotropic interactions derived from strong spin-orbit coupling.

Study of the electronic and magnetic properties as a function of isoelectronic substitution in SmFe1−xRuxAsO0.85F0.15

We have studied the electronic and magnetic properties of SmFe(1-x)RuxAsO0.85F0.15 (x = 0, 0.05, 0.25, 0.33, 0.5) by high-resolution x-ray absorption and x-ray emission spectroscopy. The local Fe magnetic moment (μ) tends to decrease for a small Ru substitution, but it shows a clear increase with further substitution. It appears that impurity scattering prevails in reducing the μ with small Ru substitution due to an extended Ru d-band. A nanoscale phase separation, that decouples the FeAs layers from the spacer layers, drives the increase of μ at higher Ru substitution. The results provide important information on nanoscale phase separation due to isoelectronic substitution in the active layers of iron-based 1111-superconductors and its effect on the local magnetic properties.