Direct Detection of Dimer Orbitals in Ba_{5}AlIr_{2}O_{11}.

The electronic states of many Mott insulators, including iridates, are often conceptualized in terms of localized atomic states such as the famous "J_{eff}=1/2 state." Although orbital hybridization can strongly modify such states and dramatically change the electronic properties of materials, probing this process is highly challenging. In this Letter, we directly detect and quantify the formation of dimer orbitals in an iridate material Ba_{5}AlIr_{2}O_{11} using resonant inelastic x-ray scattering. Sharp peaks corresponding to the excitations of dimer orbitals are observed and analyzed by a combination of density functional theory calculations and theoretical simulations based on an Ir-Ir cluster model. Such partially delocalized dimer states lead to a redefinition of the angular momentum of the electrons and changes in the magnetic and electronic behaviors of the material. We use this to explain the reduction of the observed magnetic moment with respect to predictions based on atomic states. This study opens new directions to study dimerization in a large family of materials, including solids, heterostructures, molecules, and transient states.

Magnetism in iridate heterostructures leveraged by structural distortions.

Fundamental control of magnetic coupling through heterostructure morphology is a prerequisite for rational engineering of magnetic ground states. We report the tuning of magnetic interactions in superlattices composed of single and bilayers of SrIrO3 inter-spaced with SrTiO3 in analogy to the Ruddlesden-Popper series iridates. Magnetic scattering shows predominately c-axis antiferromagnetic orientation of the magnetic moments for the bilayer, as in Sr3Ir2O7. However, the magnetic excitation gap, measured by resonant inelastic x-ray scattering, is quite different between the two structures, evidencing a significant change in the stability of the competing magnetic phases. In contrast, the single layer iridate hosts a more bulk-like gap. We find these changes are driven by bending of the c-axis Ir-O-Ir bond, which is much weaker in the single layer, and subsequent local environment changes, evidenced through x-ray diffraction and magnetic excitation modeling. Our findings demonstrate how large changes in the magnetic interactions can be tailored and probed in spin-orbit coupled heterostructures by engineering subtle structural modulations.

Quartz-based flat-crystal resonant inelastic x-ray scattering spectrometer with sub-10 meV energy resolution.

Continued improvement of the energy resolution of resonant inelastic x-ray scattering (RIXS) spectrometers is crucial for fulfilling the potential of this technique in the study of electron dynamics in materials of fundamental and technological importance. In particular, RIXS is the only alternative tool to inelastic neutron scattering capable of providing fully momentum resolved information on dynamic spin structures of magnetic materials, but is limited to systems whose magnetic excitation energy scales are comparable to the energy resolution. The state-of-the-art spherical diced crystal analyzer optics provides energy resolution as good as 25 meV but has already reached its theoretical limit. Here, we demonstrate a novel sub-10 meV RIXS spectrometer based on flat-crystal optics at the Ir-L3 absorption edge (11.215 keV) that achieves an analyzer energy resolution of 3.9 meV, very close to the theoretical value of 3.7 meV. In addition, the new spectrometer allows efficient polarization analysis without loss of energy resolution. The performance of the instrument is demonstrated using longitudinal acoustical and optical phonons in diamond, and magnon in Sr3Ir2O7. The novel sub-10 meV RIXS spectrometer thus provides a window into magnetic materials with small energy scales.

Kondo interactions from band reconstruction in YbInCu(4).

We combine resonant inelastic x-ray scattering and model calculations in the Kondo lattice compound YbInCu_{4}, a system characterized by a dramatic increase in Kondo temperature and associated valence fluctuations below a first-order valence transition at T≃42 K. The bulk-sensitive, element-specific, and valence-projected charge excitation spectra reveal an unusual quasigap in the Yb-derived state density which drives an instability of the electronic structure and renormalizes the low-energy effective Hamiltonian at the transition. Our results provide long-sought experimental evidence for a link between temperature-driven changes in the low-energy Kondo scale and the higher-energy electronic structure of this system.

Excitonic quasiparticles in a spin-orbit Mott insulator.

In condensed matter systems, out of a large number of interacting degrees of freedom emerge weakly coupled quasiparticles (QPs), in terms of which most physical properties are described. The lack of identification of such QPs is a major barrier for understanding myriad exotic properties of correlated electrons, such as unconventional superconductivity and non-Fermi liquid behaviours. Here we report the observation of a composite particle in a quasi-two-dimensional spin-1/2 antiferromagnet Sr2IrO4--an exciton dressed with magnons--that propagates with the canonical characteristics of a QP: a finite QP residue and a lifetime longer than the hopping time scale. The dynamics of this charge-neutral excitation mirrors the fundamental process of the analogous one-hole propagation in the background of spins-1/2, and reveals the same intrinsic dynamics that is obscured for a single, charged-hole doped into two-dimensional cuprates.

Tuning magnetic coupling in Sr2IrO4 thin films with epitaxial strain.

We report x-ray resonant magnetic scattering and resonant inelastic x-ray scattering studies of epitaxially strained Sr2IrO4 thin films. The films were grown on SrTiO3 and (LaAlO3)0.3(Sr2AlTaO6)0.7 substrates, under slight tensile and compressive strains, respectively. Although the films develop a magnetic structure reminiscent of bulk Sr2IrO4, the magnetic correlations are extremely anisotropic, with in-plane correlation lengths significantly longer than the out-of-plane correlation lengths. In addition, the compressive (tensile) strain serves to suppress (enhance) the magnetic ordering temperature TN, while raising (lowering) the energy of the zone-boundary magnon. Quantum chemical calculations show that the tuning of magnetic energy scales can be understood in terms of strain-induced changes in bond lengths.

Ferromagnetic exchange anisotropy from antiferromagnetic superexchange in the mixed 3d-5d transition-metal compound Sr3CuIrO6.

We report a combined experimental and theoretical study of the unusual ferromagnetism in the one-dimensional copper-iridium oxide Sr(3)CuIrO(6). Utilizing Ir L(3) edge resonant inelastic x-ray scattering, we reveal a large gap magnetic excitation spectrum. We find that it is caused by an unusual exchange anisotropy generating mechanism, namely, strong ferromagnetic anisotropy arising from antiferromagnetic superexchange, driven by the alternating strong and weak spin-orbit coupling on the 5d Ir and 3d Cu magnetic ions, respectively. From symmetry consideration, this novel mechanism is generally present in systems with edge-sharing Cu(2+)O(4) plaquettes and Ir(4+)O(6) octahedra. Our results point to unusual magnetic behavior to be expected in mixed 3d-5d transition-metal compounds via exchange pathways that are absent in pure 3d or 5d compounds.

Spin-state transition in the Fe pnictides.

We report an Fe Kß x-ray emission spectroscopy study of local magnetic moments in the rare-earth doped iron pnictide Ca(1-x)RE(x)Fe(2)As(2) (RE = La, Pr, and Nd). In all samples studied the size of the Fe local moment is found to decrease significantly with temperature and goes from ∼ 0.9 µ(B) at T = 300 K to ∼ 0.45 µ(B) at T = 70 K. In the collapsed tetragonal phase of Nd- and Pr-doped samples (T<70 K) the local moment is quenched, while the moment remains unchanged for the La-doped sample, which does not show lattice collapse. Our results show that Ca(1-x)RE(x)Fe(2)As(2) (RE = Pr and Nd) exhibits a spin-state transition and provide direct evidence for a nonmagnetic Fe(2+) ion in the collapsed tetragonal phase; spin state as predicted by Yildirim. We argue that the gradual change of the spin state over a wide temperature range reveals the importance of multiorbital physics, in particular the competition between the crystal field split Fe 3d orbitals and the Hund's rule coupling.

Crystal-field splitting and correlation effect on the electronic structure of A2IrO3.

The electronic structure of the honeycomb lattice iridates Na(2)IrO(3) and Li(2)IrO(3) has been investigated using resonant inelastic x-ray scattering (RIXS). Crystal-field-split d-d excitations are resolved in the high-resolution RIXS spectra. In particular, the splitting due to noncubic crystal fields, derived from the splitting of j(eff)=3/2 states, is much smaller than the typical spin-orbit energy scale in iridates, validating the applicability of j(eff) physics in A(2)IrO(3). We also find excitonic enhancement of the particle-hole excitation gap around 0.4 eV, indicating that the nearest-neighbor Coulomb interaction could be large. These findings suggest that both Na(2)IrO(3) and Li(2)IrO(3) can be described as spin-orbit Mott insulators, similar to the square lattice iridate Sr(2)IrO(4).

Testing the validity of the strong spin-orbit-coupling limit for octahedrally coordinated iridate compounds in a model system Sr3CuIrO6.

The electronic structure of Sr3CuIrO6, a model system for the 5d Ir ion in an octahedral environment, is studied through a combination of resonant inelastic x-ray scattering and theoretical calculations. Resonant inelastic x-ray scattering spectra at the Ir L3 edge reveal an Ir t(2g) manifold that is split into three levels, in contrast to the expectations of the strong spin-orbit-coupling limit. Effective Hamiltonian and ab inito quantum chemistry calculations find a strikingly large noncubic crystal field splitting comparable to the spin-orbit coupling, which results in a strong mixing of the j(eff)=1/2 and j(eff)=3/2 states and modifies the isotropic wave functions on which many theoretical models are based.

Large spin-wave energy gap in the bilayer iridate Sr3Ir2O7: evidence for enhanced dipolar interactions near the mott metal-insulator transition.

Using resonant inelastic x-ray scattering, we observe in the bilayer iridate Sr3Ir2O7, a spin-orbit coupling driven magnetic insulator with a small charge gap, a magnon gap of ≈92 meV for both acoustic and optical branches. This exceptionally large magnon gap exceeds the total magnon bandwidth of ≈70 meV and implies a marked departure from the Heisenberg model, in stark contrast to the case of the single-layer iridate Sr2IrO4. Analyzing the origin of these observations, we find that the giant magnon gap results from bond-directional pseudodipolar interactions that are strongly enhanced near the metal-insulator transition boundary. This suggests that novel magnetism, such as that inspired by the Kitaev model built on the pseudodipolar interactions, may emerge in small charge-gap iridates.

Magnetic excitation spectra of Sr2IrO4 probed by resonant inelastic x-ray scattering: establishing links to cuprate superconductors.

We used resonant inelastic x-ray scattering to reveal the nature of magnetic interactions in Sr2IrO4, a 5d transition-metal oxide with a spin-orbit entangled ground state and J(eff)=1/2 magnetic moments. The magnon dispersion in Sr2IrO4 is well-described by an antiferromagnetic Heisenberg model with an effective spin one-half on a square lattice, which renders the low-energy effective physics of Sr2IrO4 much akin to that in superconducting cuprates. This point is further supported by the observation of exciton modes in Sr2IrO4, whose dispersion is strongly renormalized by magnons, which can be understood by analogy to hole propagation in the background of antiferromagnetically ordered spins in the cuprates.

Probing the local order of single phospholipid membranes using grazing incidence x-ray diffraction.

We report the first grazing incidence x-ray diffraction measurements of a single phospholipid bilayer at the solid-liquid interface. Our grazing incidence x-ray diffraction and reflectivity measurements reveal that the lateral ordering in a supported DPPE (1, 2-Dipalmitoyl-sn-Glycero-3-Phosphoethanolamine) bilayer is significantly less than that of an equivalent monolayer at the air-liquid interface. Our findings also indicate that the leaflets of the bilayer are uncoupled in contrast to the scattering from free standing phosphatidylcholine bilayers. The methodology presented can be readily implemented to study more complicated biomembranes and their interaction with proteins.

Observation of a 500 meV collective mode in La2-xSrxCuO4 and Nd2CuO4 using resonant inelastic X-ray scattering.

Utilizing resonant inelastic x-ray scattering, we report a previously unobserved mode in the excitation spectrum of La2-xSrxCuO4 and Nd2CuO4 at 500 meV. The mode is peaked around the (pi, 0) point in reciprocal space and is observed to soften, and broaden, away from this point. Samples with x=0, 0.01, 0.05, and 0.17 were studied. The new mode is found to be rapidly suppressed with increasing Sr content and is absent at x=0.17, where it is replaced by a continuum of excitations. This mode is only observed when the incident x-ray polarization is normal to the CuO planes.

X-ray and ellipsometric study of strong critical adsorption.

Carpenter [Phys. Rev. E 61, 532 (2000)] succeeded in determining a single universal model, called the P1 model, that could describe the ellipsometric critical adsorption data from the liquid-vapor interface of four different critical binary liquid mixtures near their critical demixing temperatures. The P1 model also recently has been used to describe neutron reflectometry data from a critical liquid mixture/crystalline quartz interface. However, in another recent study, the P1 model failed to simultaneously describe x-ray reflectometry and ellipsometry data from the liquid-vapor surface of the critical mixture n -dodecane + tetrabromoethane (DT). In this paper, we resolve this discrepancy between x-ray and ellipsometric data for the DT system. At large length scales (far from the interface) the local concentration is described by the P1 model in order to correctly reproduce the temperature dependence of the ellipsometric data. Close to the interface, however, the molecular structure must be correctly accounted for in order to quantitatively explain the x-ray data. An important conclusion that arises from this study is that neutron or x-ray reflectometry is most sensitive to short-range interfacial structure, but may provide misleading information about long-range interfacial structure. Ellipsometry provides a more accurate measure of this long-range interfacial structure. Complex interfacial structures, possessing both short- and long-range structure, are therefore best studied using multiple techniques.

Windowless transition between atmospheric pressure and high vacuum via differential pumping for synchrotron radiation applications.

A differential pump assembly is introduced which can provide a windowless transition between the full atmospheric pressure of an in-air sample environment and the high-vacuum region of a synchrotron radiation beamline, while providing a clear aperture of approximately 1 mm to pass through the X-ray beam from a modern third-generation synchrotron radiation source. This novel pump assembly is meant to be used as a substitute for an exit vacuum window on synchrotron beamlines, where the existence of such a window would negatively impact the coherent nature of the X-ray beam or would introduce parasitic scattering, distorting weak scattering signals from samples under study. It is found that the length of beam pipe necessary to reduce atmospheric pressure to below 10 mbar is only about 130 mm, making the expected photon transmission for hard X-rays through this pipe competitive with that of a regular Be beamline window. This result is due to turbulent flow dominating the first pumping stage, providing a mechanism of strong gas conductance limitation, which is further enhanced by introducing artificial surface roughness in the pipe. Successive reduction of pressure through the transitional flow regime into the high-vacuum region is accomplished over a length of several meters, using beam pipes of increasing diameter. While the pump assembly has not been tested with X-rays, possible applications are discussed in the context of coherent and small-angle scattering.

A 2 m inelastic X-ray scattering spectrometer at CMC-XOR, Advanced Photon Source.

The design and commissioning of an inelastic X-ray scattering instrument at CMC-XOR at the Advanced Photon Source is reported. The instrument features a 2 m vertical-scattering arm with a novel counterweight design to reduce the twisting moment as the arm is moved in the scattering plane. A Ge(733) spherical analyzer was fabricated and an overall resolution of 118 meV (FWHM) was obtained with a Si(444) monochromator and a Si(111) pre-monochromator. Early results from a representative cuprate, La(2)CuO(4), are reported.

The surface structure of concentrated aqueous salt solutions.

The surface-normal electron density profile rhos(z) of concentrated aqueous salt solutions of RbBr, CsCl, LiBr, RbCl, and SrCl2 was determined by x-ray reflectivity (XR). For all but RbBr and SrCl2 rhos(z) increases monotonically with depth z from rhos(z)=0 in the vapor (z<0) to rhos(z)=rhob of the bulk (z>0) over a width of a few angstroms. The width is commensurate with the expected interface broadening by thermally excited capillary waves. Anomalous (resonant) XR of RbBr reveals a depletion at the surface of Br- ions to a depth of approximately 10 A. For SrCl2, the observed rhos(z)>rhob may imply a similar surface depletion of Cl- ions to a depth of a few angstorms. However, as the deviations of the XRs of RbBr and SrCl2 from those of the other solutions are small, the evidence for a different ion composition in the surface and the bulk is not strongly conclusive. Overall, these results contrast earlier theoretical and simulational results and nonstructural measurements, where significant surface layering of alternate, oppositely charged, ions is concluded.

Charge-transfer excitations in the model superconductor HgBa(2)CuO(4+delta).

We report a Cu -edge resonant inelastic x-ray scattering (RIXS) study of charge-transfer excitations in the 2-8 eV range in the structurally simple compound HgBa(2)CuO(4+delta) at optimal doping (T(c)=96.5 K). The spectra exhibit a significant dependence on the incident photon energy which we carefully utilize to resolve a multiplet of weakly dispersive (<0.5 eV) electron-hole excitations, including a mode at 2 eV. The observation of this 2 eV excitation suggests the existence of a remnant charge-transfer gap deep in the superconducting phase. Quite generally, our results, which include additional data for the Mott insulator La(2)CuO(4), demonstrate the importance of exploring the incident photon-energy dependence of the RIXS cross section.

X-ray specular reflectivity study of a critical binary fluid mixture.

We have used direct inversion of x-ray reflectivity data to extract the liquid-vapor interface composition profile and the related critical scaling function of a binary mixture of dodecane and tetrabromoethane. The mixture was in the one-phase region above its critical point. The results indicate the formation of a monolayer of the lower surface tension component followed by an abrupt change to a mixed composition which gradually relaxes to the bulk composition deep within the fluid.