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Cu$_2$IrO$_3$ has attracted recent interest due to its proximity to the Kitaev quantum spin liquid state and the complex structural response observed at high pressures. We use x-ray spectroscopy and scattering as well as electrical transport techniques to unveil the electronic structure of Cu$_2$IrO$_3$ at ambient and high pressures. Despite featuring a $\mathrm{Ir^{4+}}$ $J_{\rm{eff}}=1/2$ state at ambient pressure, Ir $L_{3}$ edge resonant inelastic x-ray scattering reveals broadened electronic excitations that point to the importance of Ir $5d$-Cu $3d$ interaction. High pressure first drives an Ir-Ir dimer state with collapsed $\langle \mathbf{L} \cdot \mathbf{S} \rangle$ and $\langle L_z \rangle/\langle S_z \rangle$, signaling the formation of $5d$ molecular orbitals. A novel $\mathrm{Cu \to Ir}$ charge transfer is observed at the onset of phase 5 above 30 GPa at low temperatures, leading to an approximate $\mathrm{Ir^{3+}}$ and $\mathrm{Cu^{1.5+}}$ valence, with persistent insulating electrical transport seemingly driven by charge segregation of Cu 1+/2+ ions into distinct sites. Concomitant x-ray spectroscopy and scattering measurements through different thermodynamic paths demonstrate a strong electron-lattice coupling, with $J_{\rm{eff}}=1/2$ and $\mathrm{Ir^{3+}}$/$\mathrm{Cu^{1.5+}}$ electronic states occurring only in phases 1 and 5, respectively. Remarkably, the charge-transferred state can only be reached if Cu$_2$IrO$_3$ is pressurized at low temperature, suggesting that phonons play an important role in the stability of this phase. These results point to the choice of thermodynamic path across interplanar collapse transition as a key route to access novel states in intercalated iridates., Comment: 8 pages, 4 figures, see ancillary file for Supplemental Material

Erbium-doped \ch{TiO2} materials are promising candidates for advancing quantum technologies, necessitating a thorough understanding of their electronic and crystal structures to tailor their properties and enhance coherence times. This study explored epitaxial erbium-doped rutile \ch{TiO2} films deposited on r-sapphire substrates using molecular beam epitaxy. Photoluminescence excitation spectroscopy demonstrated decreasing fluorescence lifetimes with erbium doping, indicating limited coherence times. Lattice distortions associated with \ch{Er^{3+}} were probed by X-ray absorption spectroscopy, indicating that erbium primarily occupies \ch{Ti^{4+}} sites and influences oxygen vacancies. Significant lattice distortions in the higher-order shells and full coordination around erbium suggest that additional defects are likely prevalent in these regions. These findings indicate that defects contribute to limited coherence times by introducing alternative decay pathways, leading to shorter fluorescence lifetimes., Comment: 8 pages, 13 figures, 3 tables

Spin nematic (SN) is a magnetic analog of classical liquid crystals, a fourth state of matter exhibiting characteristics of both liquid and solid. Particularly intriguing is a valence-bond SN, in which spins are quantum entangled to form a multi-polar order without breaking time-reversal symmetry, but its unambiguous experimental realization remains elusive. Here, we establish a SN phase in the square-lattice iridate Sr$_2$IrO$_4$, which approximately realizes a pseudospin one-half Heisenberg antiferromagnet (AF) in the strong spin-orbit coupling limit. Upon cooling, the transition into the SN phase at T$_C$ $\approx$ 263 K is marked by a divergence in the static spin quadrupole susceptibility extracted from our Raman spectra, and concomitant emergence of a collective mode associated with the spontaneous breaking of rotational symmetries. The quadrupolar order persists in the antiferromagnetic (AF) phase below T$_N$ $\approx$ 230 K, and becomes directly observable through its interference with the AF order in resonant x-ray diffraction, which allows us to uniquely determine its spatial structure. Further, we find using resonant inelastic x-ray scattering a complete breakdown of coherent magnon excitations at short-wavelength scales, suggesting a resonating-valence-bond-like quantum entanglement in the AF state. Taken together, our results reveal a quantum order underlying the N\'eel AF that is widely believed to be intimately connected to the mechanism of high temperature superconductivity (HTSC)., Comment: Published in https://www.nature.com/articles/s41586-023-06829-4

In the search for realizations of Quantum Spin Liquids (QSL), it is essential to understand the interplay between inherent disorder and the correlated fluctuating spin ground state. H$_3$LiIr$_2$O$_6$ is regarded as a spin liquid proximate to the Kitaev-limit (KQSL) in which H zero-point motion and stacking faults are known to be present. Bond disorder has been invoked to account for the existence of unexpected low-energy spin excitations. Controversy remains about the nature of the underlying correlated state and if any KQSL physics survives. Here, we use resonant X-ray spectroscopies to map the collective excitations in H$_3$LiIr$_2$O$_6$ and characterize its magnetic state. We uncover a broad bandwidth and momentum-independent continuum of magnetic excitations at low temperatures that are distinct from the paramagnetic state. The center energy and high-energy tail of the continuum are consistent with expectations for dominant ferromagnetic Kitaev interactions between dynamically fluctuating spins. The absence of a momentum dependence to these excitations indicates a broken translational invariance. Our data support an interpretation of H$_3$LiIr$_2$O$_6$ as a disordered topological spin liquid in close proximity to bond-disordered versions of the KQSL. Our results shed light on how random disorder affects topological magnetic states and have implications for future experimental and theoretical works toward realizing the Kitaev model in condensed matter systems

We investigate the electronic structure of two Ir$^{5+}$ honeycomb iridates, Sr$_3$CaIr$_2$O$_9$ and NaIrO$_3$, by means of resonant x-ray techniques. We confirm that Sr$_3$CaIr$_2$O$_9$ realizes a large spin-orbit driven non-magnetic $J = 0$ singlet ground state despite sizable tetragonal distortions of Ir coordinating octahedra. On the other hand, the resonant inelastic x-ray spectra of NaIrO$_3$ are drastically different from expectations for a Mott insulator with octahedrally coordinated Ir$^{5+}$. We find that the data for NaIrO$_3$ can be best interpreted as originating from a narrow gap non-magnetic $S = 0$ band insulating ground state. Our results highlight the complex role of the ligand environment in the electronic structure of honeycomb iridates and the essential role of x-ray spectroscopy to characterize electronic ground states of insulating materials.

When spin-orbit-entangled $d$-electrons reside on a honeycomb lattice, rich quantum states are anticipated to emerge, as exemplified by the $d^5$ Kitaev materials. Distinct yet equally intriguing physics may be realized with a $d$-electron count other than $d^5$. We found that the layered ruthenate Ag$_3$LiRu$_2$O$_6$ with $d^4$ Ru$^{4+}$ ions at ambient pressure forms a honeycomb lattice of spin-orbit-entangled singlets, which is a playground for frustrated excitonic magnetism. Under pressure, the singlet state does not develop the expected excitonic magnetism but experiences two successive transitions to other nonmagnetic phases, first to an intermediate phase with moderate distortion of honeycomb lattice, and eventually to a high-pressure phase with very short Ru-Ru dimer bonds. While the strong dimerization in the high-pressure phase originates from a molecular orbital formation as in the sister compound Li$_2$RuO$_3$, the intermediate phase represents a spin-orbit-coupled $J$-dimer state which is stabilized by the admixture of upper-lying $J_{\rm eff} = 1$-derived states. We argue that the $J$-dimer state is induced by a pseudo-Jahn-Teller effect associated with the low-lying spin-orbital excited states and is unique to spin-orbit-entangled $d^4$ systems. The discovery of competing singlet phases demonstrates rich spin-orbital physics of $d^4$ honeycomb compounds and paves the way for realization of unconventional magnetism., Comment: 12 pages, 5 figures

In this study, we employ bulk electronic properties characterization and x-ray scattering/spectroscopy techniques to map the structural, magnetic and electronic properties of (Eu$_{1-x}$Ca$_{x}$)$_{2}$Ir$_{2}$O$_{7}$ as a function of Ca-doping. As expected, the metal-insulator transition temperature, $T_{MIT}$, decreases with Ca-doping until a metallic state is realized down to 2 K. In contrast, $T_{AFM}$ becomes decoupled from the MIT and (likely short-range) AFM order persists into the metallic regime. This decoupling is understood as a result of the onset of an electronically phase separated state, the occurrence of which seemingly depends on both synthesis method and rare earth site magnetism. PDF analysis suggests that electronic phase separation occurs without accompanying chemical phase segregation or changes in the short-range crystallographic symmetry while synchrotron x-ray diffraction confirms that there is no change in the long-range crystallographic symmetry. X-ray absorption measurements confirm the $J_{eff}$ = 1/2 character of (Eu$_{1-x}$Ca$_{x}$)$_{2}$Ir$_{2}$O$_{7}$. Surprisingly these measurements also indicate a net electron doping, rather than the expected hole doping, indicating a compensatory mechanism. Lastly, XMCD measurements show a weak Ir magnetic polarization that is largely unaffected by Ca-doping., Comment: 18 pages, 10 figures

We use x-ray spectroscopy at Ir L$_3$/L$_2$ absorption edge to study powder samples of the intercalated honeycomb magnet Ag$_3$LiIr$_2$O$_6$. Based on x-ray absorption and resonant inelastic x-ray scattering measurements, and exact diagonalization calculations including next-neighbour Ir-Ir electron hoping integrals, we argue that the intercalation of Ag atoms results in a nearly itinerant electronic structure with enhanced Ir-O hybridization. As a result of the departure from the local relativistic $j_{\rm eff}\! = \!1/2$ state, we find that the relative orbital contribution to the magnetic moment is increased, and the magnetization density is spatially extended and asymmetric. Our results confirm the importance of metal - ligand hybridazation in the magnetism of transition metal oxides and provide empirical guidance for understanding the collective magnetism in intercalated honeycomb iridates.

$\mathrm{Cu_2IrO_3}$ is among the newest layered honeycomb iridates and a promising candidate to harbor a Kitaev quantum spin liquid state. Here, we investigate the pressure and temperature dependence of its structure through a combination of powder x-ray diffraction and x-ray absorption fine structure measurements, as well as $ab$-$initio$ evolutionary structure search. At ambient pressure, we revise the previously proposed $C2/c$ solution with a related but notably more stable $P2_1/c$ structure. Pressures below 8 GPa drive the formation of Ir-Ir dimers at both ambient and low temperatures, similar to the case of $\mathrm{Li_2IrO_3}$. At higher pressures, the structural evolution dramatically depends on temperature. A large discontinuous reduction of the Ir honeycomb interplanar distance is observed around 15 GPa at room temperature, likely driven by a collapse of the O-Cu-O dumbbells. At 15 K, pressures beyond 20 GPa first lead to an intermediate phase featuring a continuous reduction of the interplanar distance, which then collapses at 30 GPa across yet another phase transition. However, the resulting structure around 40 GPa is not the same at room and low temperatures. Remarkably, the reduction in interplanar distance leads to an apparent healing of the stacking faults at room temperature, but not at 15 K. Possible implications on the evolution of electronic structure of $\mathrm{Cu_2IrO_3}$ with pressure are discussed., Comment: 11 pages, 7 figures, see ancillary file for Supplemental Material

We report the observation of a two-dimensional (2D) checkerboard charge density wave (CDW) in the low-dimensional superconductor Ta4Pd3Te16. By determining its CDW properties across the temperature-pressure (T-P) phase diagram and comparing with prototypical CDW materials, we conclude that Ta4Pd3Te16 features: a) an incommensurate CDW with a mixed character of dimensions (Q1D considering its needle-like shape along the b-axis, Q2D as the CDW has checkerboard wavevectors, and 3D because of CDW projections along all three axes); and b) one of the weakest CDWs compared to its superconductivity (SC), i.e. enhanced SC with respect to CDW, suggesting an interesting interplay of the two orders., Comment: Z.S. and S.J.K. contributed equally to this work / Accepted for publication in Physical Review Research Rapid Communications

The effect of compression on the magnetic ground state of Sr$_2$IrO$_4$ is studied with x-ray resonant techniques in the diamond anvil cell. The weak interlayer exchange coupling between square-planar 2D IrO$_2$ layers is readily modified upon compression, with a crossover between magnetic structures around 7 GPa mimicking the effect of an applied magnetic field at ambient pressure. Higher pressures drive an order-disorder magnetic phase transition with no magnetic order detected above 17-20 GPa. The persistence of strong exchange interactions between $\mathrm{J_{eff}}=1/2$ magnetic moments within the insulating IrO$_2$ layers up to at least 35 GPa points to a highly frustrated magnetic state in compressed Sr$_2$IrO$_4$ opening the door for realization of novel quantum paramagnetic phases driven by extended $5d$ orbitals with entangled spin and orbital degrees of freedom., Comment: 4 pages, 3 figures, see ancillary file for Supplemental Material

Single crystals of a honeycomb lattice antiferromagnet, Tb$_2$Ir$_3$Ga$_9$ were synthesized, and the physical properties have been studied. From magnetometry, a long-range antiferromagnetic ordering at $\approx$12.5 K with highly anisotropic magnetic behavior was found. Neutron powder diffraction confirms that the Tb spins lie along the $\va $-axis, parallel to the shortest Tb-Tb contact. Two field-induced spin-flip transitions are observed when the field is applied parallel to this axis, separated by a plateau corresponding roughly to M$\approx$M$_{\rm{s}}$/2. Transport measurements show the resistivity to be metallic with a discontinuity at the onset of N\'eel order. Heat capacity shows a $\lambda$-like transition confirming the bulk nature of the magnetism. We propose a phenomenological spin-Hamiltonian that describes the magnetization plateau as a result of strong Ising character arising from a quasidoublet ground state of the Tb$^{3+}$ ion in a site of \textit{C$_s$} symmetry and expressing a significant bond dependent anisotropy., Comment: 11 pages, 9 figures

A pressure-induced collapse of magnetic ordering in $\beta$-Li$_2$IrO$_3$ at $P_m\sim1.5- 2$ GPa has previously been interpreted as evidence for possible emergence of spin liquid states in this hyperhoneycomb iridate, raising prospects for experimental realizations of the Kitaev model. Based on structural data obtained at \emph{room temperature}, this magnetic transition is believed to originate in small lattice perturbations that preserve crystal symmetry, and related changes in bond-directional anisotropic exchange interactions. Here we report on the evolution of the crystal structure of $\beta$-Li$_2$IrO$_3$ under pressure at low temperatures ($T\leq50$ K) and show that the suppression of magnetism coincides with a change in lattice symmetry involving Ir-Ir dimerization. The critical pressure for dimerization shifts from 4.4(2) GPa at room temperature to $\sim1.5-2$ GPa below 50 K. While a direct $Fddd \rightarrow C2/c$ transition is observed at room temperature, the low temperature transitions involve new as well as coexisting dimerized phases. Further investigation of the Ir ($L_3$/$L_2$) isotropic branching ratio in x-ray absorption spectra indicates that the previously reported departure of the electronic ground state from a $J_{\rm{eff}}=1/2$ state is closely related to the onset of dimerized phases. In essence, our results suggest that the predominant mechanism driving the collapse of magnetism in $\beta$-Li$_2$IrO$_3$ is the pressure-induced formation of Ir$_2$ dimers in the hyperhoneycomb network. The results further confirm the instability of the $J_{\rm{eff}}=1/2$ moments and related non-collinear spiral magnetic ordering against formation of dimers in the low-temperature phase of compressed $\beta$-Li$_2$IrO$_3$., Comment: 14 pages, 13 figures

We report the observation of multiple phonon satellite features in ultra thin superlattices of form $n$SrIrO$_3$/$m$SrTiO$_3$ using resonant inelastic x-ray scattering. As the values of $n$ and $m$ vary the energy loss spectra show a systematic evolution in the relative intensity of the phonon satellites. Using a closed-form solution for the cross section, we extract the variation in the electron-phonon coupling strength as a function of $n$ and $m$. Combined with the negligible carrier doping into the SrTiO$_3$ layers, these results indicate that tuning of the electron-phonon coupling can be effectively decoupled from doping. This work showcases both a feasible method to extract the electron-phonon coupling in superlattices and unveils a potential route for tuning this coupling which is often associated with superconductivity in SrTiO$_3$-based systems., Comment: 4 pages, 5 figures

In this work we analyse the role of a thin Cr spacer between Fe and Gd layers on structure and magnetic properties of a [Fe(35A)/Cr(tCr)/Gd(50A)/Cr(tCr)]x12 superlattice. Samples without the Cr spacer (tCr=0) and with a thin tCr=4A are investigated using X-ray diffraction, polarized neutron and resonance X-ray magnetic reflectometry, SQUID magnetometery, magneto-optical Kerr effect and ferromagnetic resonance techniques. Magnetic properties are studied experimentally in a wide temperature range 4-300K and analysed theoretically using numerical simulation on the basis of the mean-field model. We show that a reasonable agreement with the experimental data can be obtained considering temperature dependence of the effective field parameter in gadolinium layers. The analysis of the experimental data shows that besides a strong reduction of the antiferromagnetic coupling between Fe and Gd, the introduction of Cr spacers into Fe/Gd superlattice leads to modification of both structural and magnetic characteristics of the ferromagnetic layers.

We report on the selective fabrication of high-quality Sr$_2$IrO$_4$ and SrIrO$_3$ epitaxial thin films from a single polycrystalline Sr$_2$IrO$_4$ target by pulsed laser deposition. Using a combination of X-ray diffraction and photoemission spectroscopy characterizations, we discover that within a relatively narrow range of substrate temperature, the oxygen partial pressure plays a critical role in the cation stoichiometric ratio of the films, and triggers the stabilization of different Ruddlesden-Popper (RP) phases. Resonant X-ray absorption spectroscopy measurements taken at the Ir $L$-edge and the O $K$-edge demonstrate the presence of strong spin-orbit coupling, and reveal the electronic and orbital structures of both compounds. These results suggest that in addition to the conventional thermodynamics consideration, higher members of the Sr$_{n+1}$Ir$_n$O$_{3n+1}$ series can possibly be achieved by kinetic control away from the thermodynamic limit. These findings offer a new approach to the synthesis of ultra-thin films of the RP series of iridates and can be extended to other complex oxides with layered structure., Comment: 7 pages, 6 figures

The perovskite SrIrO3 is an exotic narrow-band metal owing to a confluence of the strengths of the spin-orbit coupling (SOC) and the electron-electron correlations. It has been proposed that topological and magnetic insulating phases can be achieved by tuning the SOC, Hubbard interactions, and/or lattice symmetry. Here, we report that the substitution of nonmagnetic, isovalent Sn4+ for Ir4+ in the SrIr1-xSnxO3 perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic (AF) phase at TN > 225 K. The continuous change of the cell volume as detected by x-ray diffraction and the lamda-shape transition of the specific heat on cooling through TN demonstrate that the metal-insulator transition is of second-order. Neutron powder diffraction results indicate that the Sn substitution enlarges an octahedral-site distortion that reduces the SOC relative to the spin-spin exchange interaction and results in the type-G AF spin ordering below TN. Measurement of high-temperature magnetic susceptibility shows the evolution of magnetic coupling in the paramagnetic phase typical of weak itinerant-electron magnetism in the Sn-substituted samples. A reduced structural symmetry in the magnetically ordered phase leads to an electron gap opening at the Brillouin zone boundary below TN in the same way as proposed by Slater., Comment: 15 pages, 4 figures

We report on the tuning of magnetic interactions in superlattices composed of single and bilayer SrIrO$_3$ inter-spaced with SrTiO$_3$. Magnetic scattering shows predominately $c$-axis antiferromagnetic orientation of the magnetic moments for the bilayer justifying these systems as viable artificial analogues of the bulk Ruddlesden-Popper series iridates. Magnon gaps are observed in both superlattices, with the magnitude of the gap in the bilayer being reduced to nearly half that in its bulk structural analogue, Sr$_3$Ir$_2$O$_7$. We assign this to modifications in the anisotropic exchange driven by bending of the $c$-axis Ir-O-Ir bond and subsequent local environment changes, as detected by x-ray diffraction and modeled using spin wave theory. These findings explain how even subtle structural modulations driven by heterostructuring in iridates are leveraged by spin orbit coupling to drive large changes in the magnetic interactions., Comment: 5 pages, 4 figures

We explore the response of Ir $5d$ orbitals to pressure in $\beta$-$\mathrm{Li_2IrO_3}$, a hyperhoneycomb iridate in proximity to a Kitaev quantum spin liquid (QSL) ground state. X-ray absorption spectroscopy reveals a reconstruction of the electronic ground state below 2 GPa, the same pressure range where x-ray magnetic circular dichroism shows an apparent collapse of magnetic order. The electronic reconstruction, which manifests a reduction in the effective spin-orbit (SO) interaction in $5d$ orbitals, pushes $\beta$-$\mathrm{Li_2IrO_3}$ further away from the pure $J_{\rm eff}=1/2$ limit. Although lattice symmetry is preserved across the electronic transition, x-ray diffraction shows a highly anisotropic compression of the hyperhoneycomb lattice which affects the balance of bond-directional Ir-Ir exchange interactions driven by spin-orbit coupling at Ir sites. An enhancement of symmetric anisotropic exchange over Kitaev and Heisenberg exchange interactions seen in theoretical calculations that use precisely this anisotropic Ir-Ir bond compression provides one possible route to realization of a QSL state in this hyperhoneycomb iridate at high pressures.

We report an experimental investigation of the two-dimensional ${J}_{\rm eff}$ = 1/2 antiferromagnetic Mott insulator by varying the interlayer exchange coupling in [(SrIrO$_3$)$_1$, (SrTiO$_3$)$_m$] ($m$ = 1, 2 and 3) superlattices. Although all samples exhibited an insulating ground state with long-range magnetic order, temperature-dependent resistivity measurements showed a stronger insulating behavior in the $m$ = 2 and $m$ = 3 samples than the $m$ = 1 sample which displayed a clear kink at the magnetic transition. This difference indicates that the blocking effect of the excessive SrTiO$_3$ layer enhances the effective electron-electron correlation and strengthens the Mott phase. The significant reduction of the Neel temperature from 150 K for $m$ = 1 to 40 K for $m$ = 2 demonstrates that the long-range order stability in the former is boosted by a substantial interlayer exchange coupling. Resonant x-ray magnetic scattering revealed that the interlayer exchange coupling has a switchable sign, depending on the SrTiO$_3$ layer number $m$, for maintaining canting-induced weak ferromagnetism. The nearly unaltered transition temperature between the $m$ = 2 and the $m$ = 3 demonstrated that we have realized a two-dimensional antiferromagnet at finite temperatures with diminishing interlayer exchange coupling., Comment: 4 figures

The simultaneous presence of sizable spin-orbit interactions and electron correlations in iridium oxides has led to predictions of novel ground states including Dirac semimetals, Kitaev spin liquids, and superconductivity. Electron and hole doping studies of spin-orbit assisted Mott insulator Sr2IrO4 are being intensively pursued due to extensive parallels with the La2CuO4 parent compound of Cuprate superconductors. In particular, the mechanism of charge doping associated with replacement of Ir with Rh ions remains controversial with profound consequences for the interpretation of electronic structure and transport data. Using x-ray absorption near edge structure (XANES) measurements at the Rh L, K- and Ir L- edges we observe anomalous evolution of charge partitioning between Rh and Ir with Rh doping. The partitioning of charge between Rh and Ir sites progresses in a way that holes are initially doped into the Jeff=1/2 band at low x only to be removed from it at higher x values. This anomalous hole doping naturally explains the re-entrant insulating phase in the phase diagram of Rh doped Sr2IrO4 and ought to be considered when searching for superconductivity and other emergent phenomena in iridates doped with 4d elements, Comment: Accepted to be published in PRB Rapid Communications, https://journals.aps.org/prb/accepted/75073OcbL8cE901092c69c34262f259d8151b3cff

We study the spin-dependent electronic structure of UTe and UT_{2}Si_{2} (T=Cu and Mn) compounds with a combination of x-ray magnetic circular dichroism measurements and first principle calculations. By exploiting the presence of sizable quadrupolar and dipolar contributions to the U L_{2,3}-edge x-ray absorption cross section we are able to provide unique information on the extent of hybridization between 5f and 6d/3d electronic states, a key parameter regulating the physical properties of all actinide materials. Since this information is hardly accessible to other probes, the new methodology opens up new venues for investigating this important class of materials., Comment: 5 pages, 3 figures

The unusual magnetic and electronic ground states of 5d iridates has been shown to be driven by intrinsically enhanced spin-orbit coupling (SOC). The influence of appreciable but reduced SOC in creating the manifested magnetic insulating states in 4d oxides is less clear, with one hurdle being the existence of such compounds. Here we present experimental and theoretical results on Sr$_4$RhO$_6$ that reveal SOC dominated behavior. Neutron measurements show the octahedra are both spatially separated and locally ideal, making the electronic ground state susceptible to alterations by SOC. Magnetic ordering is observed with a similar structure to an analogous ${J}_{\mathrm{eff}}\mathbf{=}1/2$ Mott iridate. We consider the underlying role of SOC in this rhodate with density functional theory and x-ray absorption spectroscopy and find a magnetic insulating ground state with ${J}_{\mathrm{eff}}\mathbf{=}1/2$ character.

We investigate the magnetic and electronic properties of the Gd$T_2$Zn$_{20}$ ($T$ = Fe and Co) compounds using X-ray resonant magnetic scattering (XRMS), X-ray absorption near-edge structure (XANES) and X-ray magnetic circular dichroism (XMCD) techniques. The XRMS measurements reveal that the GdCo$_2$Zn$_{20}$ compound has a commensurate antiferromagnetic spin structure with a magnetic propagation vector $\vec{\tau}$ = $(\frac{1}{2},\frac{1}{2},\frac{1}{2})$ below the N\'eel temperature ($T_N \sim$ 5.7 K). Only the Gd ions carry a magnetic moment forming an antiferromagnetic structure with magnetic representation $\Gamma_6$. For the ferromagnetic GdFe$_2$Zn$_{20}$ compound, an extensive investigation was performed at low temperature and under magnetic field using XANES and XMCD techniques. A strong XMCD signal of about 12.5 $\%$ and 9.7 $\%$ is observed below the Curie temperature ($T_C \sim$ 85 K) at the Gd-$L_2$ and $L_3$ edges, respectively. In addition, a small magnetic signal of about 0.06 $\%$ of the jump is recorded at the Zn $K$-edge suggesting that the Zn 4$p$ states are spin polarized by the Gd 5$d$ extended orbitals.

We investigate the magnetic properties of the series Sr2Ir1-xRuxO4 with neutron, resonant x-ray and magnetization measurements. The results indicate an evolution and coexistence of magnetic structures via a spin flop transition from ab-plane to c-axis collinear order as the 5d Ir4+ ions are replaced with an increasing concentration of 4d Ru4+ ions. The magnetic structures within the ordered regime of the phase diagram (x<0.3) are reported. Despite the changes in magnetic structure no alteration of the Jeff=1/2 ground state is observed. The behavior of Sr2Ir1-xRuxO4 is consistent with electronic phase separation and diverges from a standard scenario of hole doping. The role of lattice alterations with doping on the magnetic and insulating behavior is considered. The results presented here provide insight into the magnetic insulating states in strong spin-orbit coupled materials and the role perturbations play in altering the behavior.

X-ray magnetic circular dichroism (XMCD) measurements on single-crystal and powder samples of Ba$_{0.6}$K$_{0.4}$Mn$_{2}$As$_{2}$ show that the ferromagnetism below $T_{\textrm{C}}\approx$ 100 K arises in the As $4p$ conduction band. No XMCD signal is observed at the Mn x-ray absorption edges. Below $T_{\textrm{C}}$, however, a clear XMCD signal is found at the As $K$ edge which increases with decreasing temperature. The XMCD signal is absent in data taken with the beam directed parallel to the crystallographic $\textrm{c}$ axis indicating that the orbital magnetic moment lies in the basal plane of the tetragonal lattice. These results show that the previously reported itinerant ferromagnetism is associated with the As $4p$ conduction band and that distinct local-moment antiferromagnetism and itinerant ferromagnetism with perpendicular easy axes coexist in this compound at low temperature., Comment: 6 pages; Supplemental Material Included; The text in version 2 is slightly different from the text in version 1

In previous studies the pressure dependence of the magnetic ordering temperature $T_{\text{o}}$ of Dy was found to exhibit a sharp increase above its volume collapse pressure of 73 GPa, appearing to reach temperatures well above ambient at 157 GPa. In a search for a second such lanthanide, electrical resistivity measurements were carried out on neighboring Tb to 141 GPa over the temperature range 3.8 - 295 K. Below Tb's volume collapse pressure of 53 GPa, the pressure dependence $T_{\text{o}}(P)$ mirrors that of both Dy and Gd. However, at higher pressures $T_{\text{o}}(P)$ for Tb becomes highly anomalous. This result, together with the very strong suppression of superconductivity by dilute Tb ions in Y, suggests that extreme pressure transports Tb into an unconventional magnetic state with an anomalously high magnetic ordering temperature.

The ability to tune exchange (magnetic) interactions between 3d transition metals in perovskite structures has proven to be a powerful route to discovery of novel properties. Here we demonstrate that the introduction of 3d-5d exchange pathways in double perovskites enables additional tunability, a result of the large spatial extent of 5d wave functions. Using x-ray probes of magnetism and structure at high pressure, we show that compression of Sr2FeOsO6 drives an unexpected continuous change in the sign of Fe-Os exchange interactions and a transition from antiferromagnetic to ferrimagnetic order. We analyze the relevant electron-electron interactions, shedding light into fundamental differences with the more thoroughly studied 3d-3d systems.

Alkali metals display unexpected properties at high pressure, including emergence of low symmetry crystal structures, that appear to occur due to enhanced electronic correlations among the otherwise nearly-free conduction electrons. We investigate the high pressure electronic and structural ground state of K, Rb, and Cs using x-ray absorption spectroscopy and x-ray diffraction measurements together with ab initio theoretical calculations. The sequence of phase transitions under pressure observed at low temperature is similar in all three heavy alkalis except for the absence of the oC84 phase in Cs. Both the experimental and theoretical results point to pressure-enhanced localization of the valence electrons characterized by pseudo-gap formation near the Fermi level and strong spd hybridization. Although the crystal structures predicted to host magnetic order in K are not observed, the localization process appears to drive these alkalis closer to a strongly correlated electron state., Comment: 10 pages, 8 figures

With current research efforts shifting towards the 4$d$ and 5$d$ transition metal oxides, understanding the evolution of the electronic and magnetic structure as one moves away from 3$d$ materials is of critical importance. Here we perform X-ray spectroscopy and electronic structure calculations on $A$-site ordered perovskites with Cu in the $A$-site and the $B$-sites descending along the 9th group of the periodic table to elucidate the emerging properties as $d$-orbitals change from partially filled 3$d$, 4$d$, to 5$d$. The results show that when descending from Co to Ir the charge transfers from the cuprate like Zhang-Rice state on Cu to the t$_{2g}$ orbital of the B site. As the Cu $d$-orbital occupation approaches the Cu$^{2+}$ limit, a mixed-valence state in CaCu$_3$Rh$_4$O$_{12}$ and heavy fermion state in CaCu$_3$Ir$_4$O$_{12}$ are obtained. The investigated d-electron compounds are mapped onto the Doniach phase diagram of the competing RKKY and Kondo interactions developed for f-electron systems., Comment: 4 pages, 4 figures

In an attempt to destabilize the magnetic state of the heavy lanthanides Dy and Gd, extreme pressures were applied in an electrical resistivity measurement to 157 GPa over the temperature range 5 - 295 K. The magnetic ordering temperature $T_{\text{o}}$ and spin-disorder resistance $R_{sd}$ of Dy, as well as the superconducting pair-breaking effect $\Delta T_{c}$ in Y(1 at.\% Dy), are found to track each other in a highly non-monotonic fashion as a function of pressure, all three increasing sharply above 73 GPa, the critical pressure for a 6\% volume collapse in Dy. At 157 GPa $T_{\text{o}}$ is estimated to reach temperatures in the range 370 - 500 K, the highest magnetic ordering temperature of any lanthanide. In contrast, $T_{\text{o}% }(P)$ for Gd shows no such sharp increase to 105 GPa. Taken together, these results suggest that pressures greater than 73 GPa transform Dy from a conventional magnetic lanthanide into a Kondo lattice system with an anomalously high magnetic ordering temperature., Comment: 4 figures, replaces arXiv:1404.4256v2

We investigate the low temperature structural and electronic properties of the type-I clathrate Eu8Ga16Ge30 under pressure using x-ray powder diffraction (XRD), x-ray absorption near-edge structure (XANES) and x-ray magnetic circular dichroism (XMCD) techniques. The XRD measurements reveal a transition to an amorphous phase above 18 GPa. Unlike previous reports on other clathrate compounds, no volume-collapse is observed prior to the crystalline-amorphous phase transition which takes place when the unit cell volume is reduced to 81% of its ambient pressure value. Fits of the pressure-dependent relative volume to a Murnaghan equation of state (EOS) yield a bulk modulus B0 = 65+-3 GPa and a pressure derivative B'0 = 3.3+-0.5. The Eu L2-edge XMCD data shows quenching of the magnetic order at the crystalline-amorphous phase transition. The XANES spectra indicate the persistence of Eu2+ valency state up to 22 GPa, therefore the suppression of XMCD intensity is due to the loss of magnetic order as a result of frustrated exchange interactions in the amorphous phase, and not due to quenching of local moments. When compared with other clathrates, the results point to the importance of guest ion-cage interactions in determining the mechanical stability of the framework structure and the critical pressure for amorphization. Finally, the crystalline structure is not found to recover after pressure release, resulting in a novel amorphous material that is at least metastable at ambient pressure and temperature.