Transport and magnetic properties of GdBaCo_{2}O_{5+x} single crystals: A cobalt oxide with square-lattice CoO_2 planes over a wide range of electron and hole doping

Single crystals of the layered perovskite GdBaCo_{2}O_{5+x} (GBCO) have been grown by the floating-zone method, and their transport, magnetic, and structural properties have been studied in detail over a wide range of oxygen contents. The obtained data are used to establish a rich phase diagram centered at the "parent'' compound GdBaCo_{2}O_{5.5} -- an insulator with Co ions in the 3+ state. An attractive feature of GBCO is that it allows a precise and continuous doping of CoO_{2} planes with either electrons or holes, spanning a wide range from the charge-ordered insulator at 50% electron doping (x=0) to the undoped band insulator (x=0.5), and further towards the heavily hole-doped metallic state. This continuous doping is clearly manifested in the behavior of thermoelectric power which exhibits a spectacular divergence with approaching x=0.5, where it reaches large absolute values and abruptly changes its sign. At low temperatures, the homogeneous distribution of doped carriers in GBCO becomes unstable, and both the magnetic and transport properties point to an intriguing nanoscopic phase separation. We also find that throughout the composition range the magnetic behavior in GBCO is governed by a delicate balance between ferromagnetic (FM) and antiferromagnetic (AF) interactions, which can be easily affected by temperature, doping, or magnetic field, bringing about FM-AF transitions and a giant magnetoresistance (MR) phenomenon. An exceptionally strong uniaxial anisotropy of the Co spins, which dramatically simplifies the possible spin arrangements, together with the possibility of continuous ambipolar doping turn GBCO into a model system for studying the competing magnetic interactions, nanoscopic phase separation and accompanying magnetoresistance phenomena.Comment: 31 pages, 32 figures, submitted to Phys. Rev.

Room-temperature tuning of magnetic anisotropy in samarium-thulium orthoferrites

Rare-earth orthoferrites (RFeO3) provide a flexible playground for magnetic materials design, combining the magnetic properties arising from complex interactions between R3+ and Fe3+ cations within the robust framework of the perovskite structure. The most important magnetic property common to most orthoferrites is a spin reorientation transition in which the magnetic moments of Fe3+ cations rotate with respect to a crystallographic axis. SmFeO3 is unique among orthoferrites due to its high-temperature spin reorientation. It is possible to tune the spin reorientation transition to occur at room temperature by replacing Sm with Tm in the Sm0.70Tm0.30FeO3 perovskite. In this study, we show how small changes in composition in the Sm1-xTmxFeO3 (x=0.30-0.50) series provide a high degree of control over the magnetic properties. This work also offers a rather unusual look into the magnetic structure of a samarium-based perovskite by means of neutron powder diffraction, which was made possible by using Sm152. The combination of these results and magnetization measurements allowed the construction of the magnetic phase diagram of the series.Fil: Bolletta, Juan Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Cuello, Gabriel Julio. Institut Laue Langevin; Francia. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Nassif, Vivian. Universite Grenoble Alpes; FranciaFil: Suard, Emmanuelle. Institut Laue Langevin; FranciaFil: Kurbakov, Alexander I.. No especifíca;Fil: Maignan, Antoine. No especifíca;Fil: Martin, Christine. No especifíca;Fil: Carbonio, Raul Ernesto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentin

Charge and Orbital Ordering and Spin State Transition Driven by Structural Distortion in YBaCo_2O_5

We have investigated electronic structures of antiferromagnetic YBaCo_2O_5 using the local spin-density approximation (LSDA) + U method. The charge and orbital ordered insulating ground state is correctly obtained with the strong on-site Coulomb interaction. Co^{2+} and Co^{3+} ions are found to be in the high spin (HS) and intermediate spin (IS) state, respectively. It is considered that the tetragonal to orthorhombic structural transition is responsible for the ordering phenomena and the spin states of Co ions. The large contribution of the orbital moment to the total magnetic moment indicates that the spin-orbit coupling is also important in YBaCo_2O_5.Comment: 4 pages including 4 figures, Submitted to Phys. Rev. Let

Magnetic order and spin fluctuations in the spin liquid Tb2_2Sn2_2O7_7.

We have studied the spin liquid Tb$_2$Sn$_2$O$_7$ by neutron diffraction and specific heat measurements. Below about 2 K, the magnetic correlations change from antiferromagnetic to ferromagnetic. Magnetic order settles in two steps, with a smeared transition at 1.3(1) K then an abrupt transition at 0.87(2) K. A new magnetic structure is observed, not predicted by current models, with both ferromagnetic and antiferromagnetic character. It suggests that the spin liquid degeneracy is lifted by dipolar interactions combined with a finite anisotropy along $$ axes. In the ground state, the Tb$^{3+}$ ordered moment is reduced with respect to the free ion moment (9 $\mu_{\rm B}$). The moment value of 3.3(3) $\mu_{\rm B}$ deduced from the specific heat is much smaller than derived from neutron diffraction of 5.9(1) $\mu_{\rm B}$. This difference is interpreted by the persistence of slow collective magnetic fluctuations down to the lowest temperatures

Spin state and phase competition in TbBaCo_{2}O_{5.5} and the lanthanide series LnBaCo_{2}O_{5+\delta} (0<=\delta<=1)

A clear physics picture of TbBaCo$_{2}$O$_{5.5}$ is revealed on the basis of density functional theory calculations. An antiferromagnetic (AFM) superexchange coupling between the almost high-spin Co$^{3+}$ ions competes with a ferromagnetic (FM) interaction mediated by both p-d exchange and double exchange, being responsible for the observed AFM-FM transition. And the metal-insulator transition is accompanied by an xy/xz orbital-ordering transition. Moreover, this picture can be generalized to the whole lanthanide series, and it is predicted that a few room-temperature magnetoresistance materials could be found in LnBa$_{1-x}$A$_{x}$Co$_{2}$O$_{5+\delta}$ (Ln=Ho,Er,Tm,Yb,Lu; A=Sr,Ca,Mg).Comment: 13 pages, 2 figures; to be published in Phys. Rev. B on 1st Sept. Title and Bylines are added to the revised versio

Application of Gauss's theorem to quantify localized surface emissions from airborne measurements of wind and trace gases

Airborne estimates of greenhouse gas emissions are becoming more prevalent with the advent of rapid commercial development of trace gas instrumentation featuring increased measurement accuracy, precision, and frequency, and the swelling interest in the verification of current emission inventories. Multiple airborne studies have indicated that emission inventories may underestimate some hydrocarbon emission sources in US oil- and gas-producing basins. Consequently, a proper assessment of the accuracy of these airborne methods is crucial to interpreting the meaning of such discrepancies. We present a new method of sampling surface sources of any trace gas for which fast and precise measurements can be made and apply it to methane, ethane, and carbon dioxide on spatial scales of  ∼&thinsp;1000 m, where consecutive loops are flown around a targeted source region at multiple altitudes. Using Reynolds decomposition for the scalar concentrations, along with Gauss's theorem, we show that the method accurately accounts for the smaller-scale turbulent dispersion of the local plume, which is often ignored in other average mass balance methods. With the help of large eddy simulations (LES) we further show how the circling radius can be optimized for the micrometeorological conditions encountered during any flight. Furthermore, by sampling controlled releases of methane and ethane on the ground we can ascertain that the accuracy of the method, in appropriate meteorological conditions, is often better than 10 %, with limits of detection below 5 kg h−1 for both methane and ethane. Because of the FAA-mandated minimum flight safe altitude of 150 m, placement of the aircraft is critical to preventing a large portion of the emission plume from flowing underneath the lowest aircraft sampling altitude, which is generally the leading source of uncertainty in these measurements. Finally, we show how the accuracy of the method is strongly dependent on the number of sampling loops and/or time spent sampling the source plume

Polymorphs of Rb3ScF6: X-ray and Neutron Diffraction, Solid-State NMR, and Density Functional Theory Calculations Study

The crystal structures of three polymorphs of Rb3ScF6 have been determined through a combination of synchrotron, laboratory X-ray, and neutron powder diffraction, electron diffraction, and multinuclear high-field solid-state NMR studies. The room temperature (RT; α) and medium-temperature (β) structures are tetragonal, with space groups I41/a (Z = 80) and I4/m (Z = 10) and lattice parameters a = 20.2561(4) Å, c = 36.5160(0) Å and a = 14.4093(2) Å, c = 9.2015(1) Å at RT and 187 °C, respectively. The high-temperature (γ) structure is cubic space group Fm3¯ m (Z = 4) with a = 9.1944(1) Å at 250 °C. The temperatures of the phase transitions were measured at 141 and 201 °C. The three α, β, and γRb3ScF6 phases are isostructural with the α, β, and δforms of the potassium cryolite. Detailed structural characterizations were performed by density functional theory as well as NMR. In the case of the β polymorph, the dynamic rotations of the ScF6 octahedra of both Sc crystallographic sites have been detailed. © 2021 American Chemical Society.For DFT calculations, we thank the “Centre de Calcul Scientifique en region Centre” (Orléans, France). We acknowledge the Interface, Confinement, Materials and Nanostructures (Orléans, France) for access to their transmission electron microscope. Financial support from the IR-RMN-THC Fr3050 CNRS for conducting the research is gratefully acknowledged. This study was also financially supported by VEGA-2/0060/18 and ITMS project (code 313021T081, Research & Innovation Operational Programme funded by the ERDF). We thank also Dr. F. Vivet, Dr. F. Fayon, and Dr. D. Massiot for useful discussions

Tracking a killer shrimp: Dikerogammarus villosus invasion dynamics across Europe

Aim: Invasive alien species are a growing problem worldwide due to their ecological, economic and human health impacts. The “killer shrimp” Dikerogammarus villosus is a notorious invasive alien amphipod from the Ponto-Caspian region that has invaded many fresh and brackish waters across Europe. Understandings of large-scale population dynamics of highly impactful invaders such as D. villosus are lacking, inhibiting predictions of impact and efficient timing of management strategies. Hence, our aim was to assess trends and dynamics of D. villosus as well as its impacts in freshwater rivers and streams. Location: Europe. Methods: We analysed 96 European time series between 1994 and 2019 and identified trends in the relative abundance (i.e. dominance %) of D. villosus in invaded time series, as well as a set of site-specific characteristics to identify drivers and determinants of population changes and invasion dynamics using meta-regression modelling. We also looked at the spread over space and time to estimate the invasion speed (km/year) of D. villosus in Europe. We investigated the impact of D. villosus abundance on recipient community metrics (i.e. abundance, taxa richness, temporal turnover, Shannon diversity and Pielou evenness) using generalized linear models. Results: Population trends varied across the time series. Nevertheless, community dominance of D. villosus increased over time across all time series. The frequency of occurrences (used as a proxy for invader spread) was well described by a Pareto distribution, whereby we estimated a lag phase (i.e. the time between introduction and spatial expansion) of approximately 28 years, followed by a gradual increase before new occurrences declined rapidly in the long term. D. villosus population change was associated with decreased taxa richness, community turnover and Shannon diversity. Main Conclusion: Our results show that D. villosus is well-established in European waters and its abundance significantly alters ecological communities. However, the multidecadal lag phase prior to observed spatial expansion suggests that initial introductions by D. villosus are cryptic, thus signalling the need for more effective early detection methods