Spin-orbit coupling controlled ground state in the Ir(V) perovskites A2ScIrO6 (A = Ba or Sr)

The structural and magnetic properties of the two Ir(V) perovskites Ba2ScIrO6 and Sr2ScIrO6 have been established. The structures were refined using a combined neutron and Synchrotron data set. At room temperature the former has a cubic structure in space group Fm3 ̅m a = 8.1450(3) Å and the latter is monoclinic in P21/n with a = 5.6606(3) b= 5.6366(3) c = 7.9720(4) Å β = 89.977(5)°. Magnetization measurements show both oxides have magnetic moments close to zero as a consequence of strong spin-orbit coupling that results in a Jeff ~ 0 ground state. The distortion of the IrO6 octahedra in Sr2ScIrO6 is insufficient to generate crystal field splitting strong enough to quench the spin orbit coupling.Australian Synchrotron Australian Research Counci

Magnetic and structural studies of Sc containing ruthenate double perovskites A2ScRuO6 (A = Ba, Sr).

Ruthenium containing double perovskites A2ScRuO6 have been synthesized as polycrystalline powders and structurally characterized using a combination of synchrotron X-ray and neutron powder diffraction methods. When A = Ba a hexagonal 6L perovskite structure is obtained if the synthesis is conducted at ambient pressure and a rock-salt ordered cubic structure obtained if the sample is quenched from high pressures. The Sr oxide Sr2ScRuO6 is obtained with a rock-salt ordered corner sharing topology. Heat capacity and bulk magnetic susceptibility measurements show the three oxides are antiferromagnets. Cubic Ba2ScRuO6 undergoes a metal-insulator transition near 270 K and hexagonal Ba2ScRuO6 is a semiconductor with an activation energy of 0.207 eV. The magnetic structures of the two rock-salt ordered double perovskites were established using powder neutron diffraction, and are described by k = (001) and k = (000) for the Ba and Sr oxides respectively, corresponding to type I antiferromagnetic structures, with ferromagnetic layers stacked antiferromagnetically. The ambient pressure hexagonal polymorph of Ba2ScRuO6 has partial Sc-Ru ordering at both the face-sharing B2O9 dimer and corner sharing BO6 sites. The magnetic structure is described by k = (½ 0 0) with the basis vector belonging to the irreducible representation Γ3.Australian Synchrotron Australian Research Counci

Thermal Expansion in BaRuO3 Perovskites – an unusual case of bond strengthening at high temperatures

The temperature dependence of the structures of three polytypes of BaRuO3 have been investigated between room temperature and 1000 °C using high resolution Synchrotron X-ray diffraction. The structural studies reveal a systematic decrease in the Ru-Ru distance as the pressure required to prepare the polytype increases. The O-O distance across the shared face increases as the Ru-Ru separation decreases. The 9R and 4H polytypes undergo unexceptional changes with increasing temperature. In 6H-BaRuO3 there is an apparent increase in the Ru-Ru interaction around 650 °C and concurrent reduction in the O-O distance indicating an anomalous strengthening of the Ru-Ru interactions upon heating.Australian Synchrotron Australian Research Counci

Structural and magnetic properties of the osmium double perovskites Ba2-xSrxYOsO6

The crystal and magnetic structures of double perovskites of the type Ba2-xSrxYOsO6 have been studied by synchrotron X-ray and neutron powder diffraction methods, bulk magnetic susceptibility measurements and X-ray absorption spectroscopy. The structures were refined using a combined neutron and synchrotron data set and are based on ordered array of corner sharing YO6 and OsO6 octahedra, with the Ba/Sr cations being completely disordered. The structure evolves from cubic to monoclinic as the Sr content is increased, due to the introduction of cooperative tilting of the octahedra. Bulk magnetic susceptibility measurements demonstrate the oxides are all antiferromagnets. The decrease in symmetry results in a, non-linear, increase in the Neel temperature. Low temperature neutron diffraction measurements of selected examples show these to be type-I antiferromagnets. X-ray absorption spectra collected at the Os L3- and L2-edges confirm the Os is pentavalent in all cases, and there is no detectable change in the covalency of the Os cation as the A-cation changes. Analysis of the L3:L2 branching ratio shows that the spin-orbit coupling is constant and insignificant across the series.Australian Synchrotron Australian Research Counci

Developing a set of ancestry-sensitive DNA markers reflecting continental origins of humans

Background: The identification and use of Ancestry-Sensitive Markers (ASMs), i.e. genetic polymorphisms facilitating the genetic reconstruction of geographical origins of individuals, is far from straightforward. Results: Here we describe the ascertainment and application of five different sets of 47 single nucleotide polymorphisms (SNPs) allowing the inference of major human groups of different continental origin. For this, we first used 74 cell lines, representing human males from six different geographical areas and screened them with the Affymetrix Mapping 10K assay. In addition to using summary statistics estimating the genetic diversity among multiple groups of individuals defined by geography or language, we also used the program STRUCTURE to detect genetically distinct subgroups. Subsequently, we used a pairwise FSTranking procedure among all pairs of genetic subgroups in order to identify a single best performing set of ASMs. Our initial results were independently confirmed by genotyping this set of ASMs in 22 individuals from Somalia, Afghanistan and Sudan and in 919 samples from the CEPH Human Genome Diversity Panel (HGDP-CEPH). Conclusion: By means of our pairwise population FSTranking approach we identified a set of 47 SNPs that could serve as a panel of ASMs at a continental level

Mechano-Chemical Synthesis, Structural Features and Optical Gap of Hybrid CH3NH3CdBr3 Perovskite

Hybrid methyl-ammonium (MA:CH3 NH3+) lead halide MAPbX3 (X = halogen) perovskites exhibit an attractive optoelectronic performance that can be applied to the next generation of solar cells. To extend the field of interest of these hybrid materials, we describe the synthesis by a solvent-free ball-milling procedure, yielding a well crystallized, pure and moisture stable specimen of the Cd tribromide counterpart, MACdBr3, which contains chains of face-sharing CdBr6 octahedra in a framework defined in the Cmc21 (No 36) space group. The details of the structural arrangement at 295 K have been investigated by high angular resolution synchrotron x-ray diffraction (SXRD), including the orientation of the organic MA units, which are roughly aligned along the c direction, given the acentric nature of the space group. UV-vis spectra unveil a gap of 4.6 eV, which could be useful for ultraviolet detectors.Fil: Alonso, José Antonio. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Kayser, Paula. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Hong, Bo Kyung. Instituto de Ciencia de Materiales de Madrid; EspañaFil: Álvarez Galván, María Consuelo. Consejo Superior de Investigaciones Científicas; EspañaFil: Fauth, Francois. No especifíca;Fil: Lopez, Carlos Alberto. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Área Química General e Inorgánica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Investigaciones en Tecnología Química. Universidad Nacional de San Luis. Facultad de Química, Bioquímica y Farmacia. Instituto de Investigaciones en Tecnología Química; Argentin

Dimensional crossover of correlated anion disorder in oxynitride perovskites

A simple crossover from two-dimensional to three-dimensional correlated disorder of O and N atoms on a cubic lattice has been discovered within the Ba1xSrxTaO2N series of perovskite oxynitrides. The crossover is driven by lattice expansion as x decreases, and provides a rapid increase in entropy due to a change from subextensive to extensive configurational entropy regimes.We thank STFC, UK for support for H. J. and provision of ISIS beamtime, and EPSRC for additional support. This work was also supported by the Ministerio de Economia y Competitividad (MINECO), Spain through Project MAT2017-86616-R, the Severo Ochoa Program SEV-2015-0496, and Fellowship support to AB (MAT2011-24757). We thank the ALBA synchrotron for the provision of beamtime and Prof. Rosa Palacin, Dr Carlos Frontera (ICMAB-CSIC) and Dr F. Fauth (ALBA) for assistance with data collection.Peer reviewe

Electronic structure, local magnetism, and spin-orbit effects of Ir(IV)-, Ir(V)-, and Ir(VI)-based compounds

Element- and orbital-selective x-ray absorption and magnetic circular dichroism measurements are carried out to probe the electronic structure and magnetism of Ir 5d electronic states in double perovskite Sr2MIrO6 (M=Mg, Ca, Sc, Ti, Ni, Fe, Zn, In) and La2NiIrO6 compounds. All the studied systems present a significant influence of spin-orbit interactions in the electronic ground state. In addition, we find that the Ir 5d local magnetic moment shows different character depending on the oxidation state despite the net magnetization being similar for all the compounds. Ir carries an orbital contribution comparable to the spin contribution for Ir4+ (5d5) and Ir5+ (5d4) oxides, whereas the orbital contribution is quenched for Ir6+ (5d3) samples. Incorporation of a magnetic 3d atom allows getting insight into the magnetic coupling between 5d and 3d transition metals. Together with previous susceptibility and neutron diffraction measurements, the results indicate that Ir carries a significant local magnetic moment even in samples without a 3d metal. The size of the (small) net magnetization of these compounds is a result of predominant antiferromagnetic interactions between local moments coupled with structural details of each perovskite structure.This work was partially supported by the Spanish MINECO Projects No. MAT2014-54425-R and No. MAT2013-41099-R and by the Comunidad de Madrid Project No. S2009/PPQ-1551. M. A. Laguna-Marco acknowledges CSIC and European Social Fund for a JAE-Doc contract. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357.Peer Reviewe

Structure and Magnetism in Sr1-xAxTcO3 Perovskites. The importance of the A-site cation.

The Sr1-xBaxTcO3 (x = 0, 0.1, 0.2) oxides were prepared and their solid-state and magnetic structure studied as a function of the temperature by x-ray and neutron powder diffraction. The refined Tc moments at room temperature and Nèel temperatures for Ba0.1Sr0.9TcO3 and Ba0.2Sr0.8TcO3 were 2.32(14) μβ and 2.11(13) μβ and 714 °C and 702 °C respectively. In contrast to expectations, the Nèel temperature in the series Sr1-xAxTcO3 decreases with increasing Ba content. This observation is consistent with previous experimental measurements for the two series AMO3 (M = Ru, Mn; A = Ca, Sr, Ba) where the maximum magnetic ordering temperature was observed for A = Sr. Taken with these previous results the current work demonstrates the critical role of the A-site cation in the broadening of the π* bandwidth and ultimately the magnetic ordering temperature.Australian Synchrotron Australian Research Counci