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Because of the possible crossover of Pb and 3d transition-metal (TM) redox levels, a charge transfer between Pb and TM leads to a continuous evolution from Pb2+Ti4+O3 to Pb4+Ni2+O3 in the perovskit...

In the high spin–orbit-coupled Sr2IrO4, the high sensitivity of the ground state to the details of the local lattice structure shows a large potential for the manipulation of the functional properties by inducing local lattice distortions. We use epitaxial strain to modify the Ir–O bond geometry in Sr2IrO4 and perform momentum-dependent resonant inelastic X-ray scattering (RIXS) at the metal and at the ligand sites to unveil the response of the low-energy elementary excitations. We observe that the pseudospin-wave dispersion for tensile-strained Sr2IrO4 films displays large softening along the [h,0] direction, while along the [h,h] direction it shows hardening. This evolution reveals a renormalization of the magnetic interactions caused by a strain-driven cross-over from anisotropic to isotropic interactions between the magnetic moments. Moreover, we detect dispersive electron–hole pair excitations which shift to lower (higher) energies upon compressive (tensile) strain, manifesting a reduction (increase) in the size of the charge gap. This behavior shows an intimate coupling between charge excitations and lattice distortions in Sr2IrO4, originating from the modified hopping elements between the t2g orbitals. Our work highlights the central role played by the lattice degrees of freedom in determining both the pseudospin and charge excitations of Sr2IrO4 and provides valuable information toward the control of the ground state of complex oxides in the presence of high spin–orbit coupling., Proceedings of the National Academy of Sciences of the United States of America, 117 (40), ISSN:0027-8424, ISSN:1091-6490

The interaction of high-quality transition metal trichalcogenides (TMTs) single crystals FePX3 (X: S, Se) with water molecules is studied using near-edge x-ray absorption fine structure (NEXAFS) and x-ray photoelectron spectroscopy (XPS) in a wide range of temperature and partial pressure of H2O. The physisorption nature of interaction between H2O and FePX3 is found at low temperatures and relatively small concentrations of water molecules, that is supported by the DFT results. When temperature of the FePX3 samples and partial pressure of H2O are increased, the interaction at the interface is defined by two competing processes—adsorption of molecules at high partial pressure of H2O and desorption of molecules due to the increased surface mobility and physisorption nature of interaction. Our intensive XPS/NEXAFS experiments accompanied by DFT calculations bring new understanding on the interaction of H2O with surface of a new class of 2D materials, TMTs, pointing to their stability and reactivity, that is important for further applications in different areas, like sensing and catalysis.

Developing characterization techniques and analysis methods adapted to the investigation of nanoparticles (NPs) is of fundamental importance considering the role of these materials in many fields of research. The study of actinide based NPs, despite their environmental relevance, is still underdeveloped compared to that of NPs based on stable and lighter elements. We present here an investigation of ThO2 NPs performed with High-Energy Resolution Fluorescence Detected (HERFD) X-ray Absorption Near-Edge Structure (XANES) and with ab initio XANES simulations. The first post-edge feature of Th L3 edge HERFD XANES disappears in small NPs and simulations considering non-relaxed structural models reproduce the trends observed in experimental data. Inspection of the simulations from Th atoms in the core and on the surface of the NP indeed demonstrates that the the first post-edge feature is very sensitive to the lowering of the number of coordinating atoms and therefore to the more exposed Th atoms at the surface of the NP. The sensitivity of the L3 edge HERFD XANES to low coordinated atoms at the surface stems from the hybridization of the d-Density of States (DOS) of Th with both O and Th neighboring atoms. This may be a common feature to other oxide systems that can be exploited to investigate surface interactions.

Significance Understanding the relationship between entangled degrees of freedom (DOF) is a central problem in correlated materials and the possibility to influence their balance is promising toward realizing novel functionalities. In Sr2IrO4, the interaction between spin–orbit coupling and electron correlations induces an exotic ground state with magnetotransport properties promising for antiferromagnetic spintronics applications. Moreover, the coupling between orbital and spin DOF renders the magnetic structure sensitive to the Ir–O bond environment. To date, a detailed understanding of the microscopic spin-lattice and electron–phonon interactions is still lacking. Here, we use strain engineering to perturb the local lattice environment and, by tracking the response of the low-energy elementary excitations, we unveil the response of the microscopic spin and charge interactions., In the high spin–orbit-coupled Sr2IrO4, the high sensitivity of the ground state to the details of the local lattice structure shows a large potential for the manipulation of the functional properties by inducing local lattice distortions. We use epitaxial strain to modify the Ir–O bond geometry in Sr2IrO4 and perform momentum-dependent resonant inelastic X-ray scattering (RIXS) at the metal and at the ligand sites to unveil the response of the low-energy elementary excitations. We observe that the pseudospin-wave dispersion for tensile-strained Sr2IrO4 films displays large softening along the [h,0] direction, while along the [h,h] direction it shows hardening. This evolution reveals a renormalization of the magnetic interactions caused by a strain-driven cross-over from anisotropic to isotropic interactions between the magnetic moments. Moreover, we detect dispersive electron–hole pair excitations which shift to lower (higher) energies upon compressive (tensile) strain, manifesting a reduction (increase) in the size of the charge gap. This behavior shows an intimate coupling between charge excitations and lattice distortions in Sr2IrO4, originating from the modified hopping elements between the t2g orbitals. Our work highlights the central role played by the lattice degrees of freedom in determining both the pseudospin and charge excitations of Sr2IrO4 and provides valuable information toward the control of the ground state of complex oxides in the presence of high spin–orbit coupling.

We use resonant inelastic x-ray scattering (RIXS) at the Ir L3 edge to study the effect of hole doping upon the Jeff=1/2 Mott-insulating state in Sr2IrO4, via Rh replacement of the Ir site. The spin-wave gap, associated with XY-type spin-exchange anisotropy, collapses with increasing Rh content, prior to the suppression of the Mott-insulating state and in contrast to electron doping via La substitution of the Sr site. At the same time, despite heavy damping, the d-d excitation spectra retain their overall amplitude and dispersion character. A careful study of the spin-wave spectrum reveals that deviations from the J1-J2-J3 Heisenberg used to model the pristine system disappear at intermediate doping levels. These findings are interpreted in terms of a modulation of Ir-Ir correlations due to the influence of Rh impurities upon nearby Ir wave functions, even as the single-band Jeff=1/2 model remains valid up to full carrier delocalization. They underline the importance of the transition metal site symmetry when doping pseudospin systems such as Sr2IrO4., Comment: 5 pages, 3 figures

Developing characterization techniques and analysis methods adapted to the investigation of nanoparticles (NPs) is of fundamental importance considering the role of these materials in many fields of research. The study of actinide based NPs, despite their environmental relevance, is still underdeveloped compared to that of NPs based on stable and lighter elements. We present here an investigation of ThO

Investigation of elementary excitations has advanced our understanding of many-body physics governing most physical properties of matter. Recently spin-orbit excitons have drawn much attention, whose condensates near phase transitions exhibit Higgs mode oscillations, a long-sought physical phenomenon [Nat. Phys. {\bf 13}, 633 (2017)]. These critical transition points resulting from competing spin-orbit coupling (SOC), local crystalline symmetry and exchange interactions, are not obvious in Iridium based materials, where SOC prevails in general. Here, we present results of resonant inelastic x-ray scattering on a spin-orbital liquid Ba$_3$ZnIr$_2$O$_9$ and three other 6H-hexagonal perovskite iridates which show magnetism, contrary to non-magnetic singlet ground state expected due to strong SOC. Our results show that substantial hopping between closely placed Ir$^{5+}$ ions within Ir$_2$O$_9$ dimers in these 6H-iridates, modifies spin-orbit coupled states and reduces spin-orbit excitation energies. Here, we are forced to use at least a two-site model, to match the excitation spectrum going in line with the strong intra-dimer hopping. Apart from SOC, low energy physics of iridates is thus critically dependent on hopping, and may not be ignored even for systems having moderate hopping, where the excitation spectra can be explained using an atomic model. SOC which is generally found to be 0.4-0.5~eV in iridates, is scaled in effect down to $\sim$0.26~eV for the 6H-systems, sustaining the hope to achieve quantum criticality by tuning Ir-Ir separation., Comment: 12 Pages, Main text has 4 figures, SI which is added at the end of the main text has 5 figures and two tables

Spin-orbit entangled magnetic dipoles, often referred to as pseudospins, provide a new avenue to explore novel magnetism inconceivable in the weak spin-orbit coupling limit, but the nature of their low-energy interactions remains to be understood. We present a comprehensive study of the static magnetism and low-energy pseudospin dynamics in the archetypal spin-orbit Mott insulator Sr2IrO4. We find that in order to understand even basic magnetization measurements, a formerly overlooked in-plane anisotropy is fundamental. In addition to magnetometry, we use neutron diffraction, inelastic neutron scattering and resonant elastic and inelastic x-ray scattering to identify and quantify the interactions that determine the global symmetry of the system and govern the linear responses of pseudospins to external magnetic felds and their low-energy dynamics. We find that a pseudospin-only Hamiltonian is insufficient for an accurate description of the magnetism in Sr2IrO4 and that pseudospin-lattice coupling is essential. This finding should be generally applicable to other pseudospin systems with sizable orbital moments sensitive to anisotropic crystalline environments., Main text:11 pages, 12 figures Supplementary Material: 3 pages, 2 figures, 1 table

While it was speculated that $5{d}^{4}$ systems would possess nonmagnetic $J=0$ ground state due to strong spin-orbit coupling (SOC), all such systems have invariably shown the presence of magnetic moments so far. A puzzling case is that of ${\mathrm{Ba}}_{2}{\mathrm{YIrO}}_{6}$, which in spite of having a perfectly cubic structure with largely separated ${\mathrm{Ir}}^{5+}\phantom{\rule{4pt}{0ex}}({d}^{4})$ ions, has consistently hosted weak magnetic moments. We show from muon spin relaxation $(\ensuremath{\mu}\mathrm{SR})$ measurements that a change in the magnetic environment of the implanted muons in ${\mathrm{Ba}}_{2}{\mathrm{YIrO}}_{6}$ occurs as the temperature is lowered below 10 K indicating magnetic response has a temperature dependence unlikely for a $J=0$ system. Interestingly, the estimated value of SOC obtained by fitting the resonant inelastic x-ray scattering (RIXS) spectrum of ${\mathrm{Ba}}_{2}{\mathrm{YIrO}}_{6}$ with an effective atomic many-body Hamiltonian is found to be as high as 0.39 eV, comparable to the reported value of SOC in other magnetic ${d}^{4}$ iridates with noncubic distortion. We argue that in addition to strong SOC, the presence of intersite hopping triggers delocalization of holes, resulting in the spontaneous generation of magnetic moments. Our theoretical calculations further indicate that these moments favor the formation of spin-orbital singlets in the case of ${\mathrm{Ba}}_{2}{\mathrm{YIrO}}_{6}$, which is manifested in $\ensuremath{\mu}\mathrm{SR}$ experiments measured down to 60 mK.