Spin-orbital ordering and mesoscopic phase separation in the double perovskite Ca2FeReO6

Neutron powder diffraction measurements on Ca2FeReO6 reveal that this double perovskite orders ferrimagnetically and shows anomalous lattice parameter behavior below T-C=521 K. Below similar to300 K and similar to160 K we observe that the high-T monoclinic crystal structure separates into two and three monoclinic phases, respectively. A magnetic field suppresses the additional phases at low T in favor of the highest-T phase. These manifestations of the orbital degree of freedom of Re 5d electrons indicate that these electrons are strongly correlated and the title compound is a Mott insulator, with competing spin-orbitally ordered states.

Influence of the highest occupied molecular orbital energy level of the donor material on the effectiveness of the anode buffer layer in organic solar cells

Efficiency of organic photovoltaic cells based on organic electron donor/organic electron acceptor junctions can be strongly improved when the transparent conductive Anode is coated with a Buffer Layer (ABL). Here, the effects of a metal (gold) or oxide (molybdenum oxide) ABL are reported, as a function of the Highest Occupied Molecular Orbital (HOMO) of different electron donors. The results indicate that a good matching between the work function of the anode and the highest occupied molecular orbital of the donor material is the major factor limiting the hole transfer efficiency. Indeed, gold is efficient as ABL only when the HOMO of the organic donor is close to its work function Phi(Au). Therefore we show that the MoO(3) oxide has a wider field of application as ABL than gold. (C) 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Tuning of dielectric properties and magnetism of SrTiO(3) by site-specific doping of Mn

Combining experiments with first-principles calculations, we show that site-specific doping of Mn into SrTiO(3) has a decisive influence on the dielectric properties of these doped systems. We find that phonon contributions to the dielectric constant invariably decrease sharply on doping at any site. However, a sizable, random dipolar contribution only for Mn at the Sr site arises from a strong off-centric displacement of Mn in spite of Mn being in a non-d(0) state; this leads to a large dielectric constant at higher temperatures and gives rise to a relaxor ferroelectric behavior at lower temperatures. We also investigate magnetic properties in detail and critically reevaluate the possibility of a true multiglass state in such systems.

Form, Content, and Magnetism in Iron Oxide Nanocrystals

Monodisperse iron oxide nanocrystals with spherical and cubic morphologies, of comparable dimensions, have been prepared by the thermal decomposition of FeOOH. The lattice spacings of both forms agree with that of magnetite, Fe(3)O(4). The two, however, exhibit very different blocking temperatures. Nanocrystals of cubic morphology are superparamagnetic above 190 K while the spherical nanocrystals at a lower temperature, 142 K. The higher blocking temperatures in particles of cubic morphology are shown to be a consequence of exchange bias fields. We show that in the present iron oxide nanocrystals the exchange bias fields originate from the presence of trace amounts of wustite, FeO. A Reitveld refinement analysis of the X-ray diffraction patterns shows that nanocrystals of cubic morphology have a higher FeO content. The higher FeO content is responsible for the larger exchange bias fields that in turn lead to a higher blocking temperature for nanocrystals with cubic morphology.

Energy-dependent orbital modulation of X-rays and constraints on emission of the jet in Cyg X-3

We study the orbital modulation of X-rays from Cyg X-3, using data from Swift, INTEGRAL and RXTE. Using the wealth of data presently available and an improved averaging method, we obtain energy-dependent folded and averaged light curves with unprecedented accuracy. We find that above similar to 5?keV the modulation depth decreases with increasing energy, which is consistent with the modulation being caused by both boundfree absorption and Compton scattering in the stellar wind of the donor, with minima corresponding to the highest optical depth, which occurs around the superior conjunction. We find a decrease of the depth below similar to 3?keV, which appears to be due to re-emission of the absorbed continuum by the wind in soft X-ray lines. Based on the shape of the folded light curves, any X-ray contribution from the jet in Cyg X-3, which emits ?-rays detected at energies >0.1?GeV in the soft spectral states, is found to be minor up to similar to 100?keV. This implies the presence of a rather sharp low-energy break in the jet MeV-range spectrum. We also calculate phase-resolved RXTE X-ray spectra and show that the difference between the spectra corresponding to phases around superior and inferior conjunctions can indeed be accounted for by the combined effect of boundfree absorption in an ionized medium and Compton scattering.

Sensory-organ-like response determines the magnetism of zigzag-edged honeycomb nanoribbons

We present an analytical effective theory for the magnetic phase diagram for zigzag-edge terminated honeycomb nanoribbons described by a Hubbard model with an interaction parameter U. We show that the edge magnetic moment varies as ln U and uncover its dependence on the width W of the ribbon. The physics of this owes its origin to the sensory-organ-like response of the nanoribbons, demonstrating that considerations beyond the usual Stoner-Landau theory are necessary to understand the magnetism of these systems. A first-order magnetic transition from an antiparallel orientation of the moments on opposite edges to a parallel orientation occurs upon doping with holes or electrons. The critical doping for this transition is shown to depend inversely on the width of the ribbon. Using variational Monte Carlo calculations, we show that magnetism is robust to fluctuations. Additionally, we show that the magnetic phase diagram is generic to zigzag-edge terminated nanostructures such as nanodots. Furthermore, we perform first-principles modeling to show how such magnetic transitions can be realized in substituted graphene nanoribbons. DOI: 10.1103/PhysRevB.87.085412

New rock salt-related oxides Li3M2RuO6 (M=Co, Ni): Synthesis, structure, magnetism and electrochemistry

We describe the synthesis, crystal structure, magnetic and electrochemical characterization of new rock salt-related oxides of formula, Li3M2RuO6 (M=Co, Ni). The M=Co oxide adopts the LiCoO2 (R-3m) structure, where sheets of LiO6 and (Co-2/Ru)O-6 octahedra are alternately stacked along the c-direction. The M=Ni oxide also adopts a similar layered structure related to Li2TiO3, where partial mixing of Li and Ni/Ru atoms lowers the symmetry to monoclinic (C2/c). Magnetic susceptibility measurements reveal that in Li3Co2RuO6, the oxidation states of transition metal ions are Co3+ (S=0), Co2+ (S=1/2) and Ru4+ (S=1), all of them in low-spin configuration and at 10 K, the material orders antiferromagnetically. Analogous Li3Ni2RuO6 presents a ferrimagnetic behavior with a Curie temperature of 100 K. The differences in the magnetic behavior have been explained in terms of differences in the crystal structure. Electrochemical studies correlate well with both magnetic properties and crystal structure. Li-transition metal intermixing may be at the origin of the more impeded oxidation of Li3Ni2RuO6 when compared to Li3CO2RuO6. Interestingly high first charge capacities (between ca. 160 and 180 mAh g(-1)) corresponding to ca. 2/3 of theoretical capacity are reached albeit, in both cases, capacity retention and cyclability are not satisfactory enough to consider these materials as alternatives to LiCoO2. (C) 2013 Elsevier Inc. All rights reserved.

Anomalous magnetism of Pr in PrCoAsO

Detailed magnetization and magneto-transport measurements studies are carried out to unearth the anomalous magnetism of Pr in PrCoAsO compound. The studied PrCoAsO sample is single phase and crystallized in the tetragonal structure with space group P4/nmm in analogy of ZrCuSiAs type compounds. Detailed magnetization measurements showed that Co moments in PrCoAsO exhibit weakly itinerant ferromagnetic Co spins ordering at below 80 K with a small magnetic moments of similar to 0.12 mu B/f.u. High temperatures Curie-Weiss fit, resulted in effective paramagnetic moment mu(eff) (exp) of 5.91 mu(B)/f.u., which can be theoretically assigned to 3d Co (3.88 mu(B)) and 4f Pr (3.58 mu(B)). Further, a positive Curie-Weiss temperature (Theta) of 136 K is seen, indicating predominant ferromagnetic interactions in PrCoAsO. Detailed transport measurements showed that PrCoAsO exhibit metallic behavior and negative magneto-resistance below ferro-magnetically (FM) ordered state. Surprisingly, the situation of PrCoAsO is similar to non magnetic La containing LaCoAsO and strikingly different than that as reported for magnetic Nd, Sm and Gd i.e., (Nd/Sm/Gd)CoAsO. The magnetic behavior of PrCoAsO being closed to LaCoAsO and strikingly different to that of (Nd/Sm/Gd)CoAsO is unusual. (C) 2014 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

Orbital phase resolved spectroscopy of GX 301-2 with MAXI

GX 301-2, a bright high-mass X-ray binary with an orbital period of 41.5 d, exhibits stable periodic orbital intensity modulations with a strong pre-periastron X-ray flare. Several models have been proposed to explain the accretion at different orbital phases, invoking accretion via stellar wind, equatorial disc, and accretion stream from the companion star. We present results from exhaustive orbital phase resolved spectroscopic measurements of GX 301-2 using data from the Gas Slit Camera onboard MAXI. Using spectroscopic analysis of the MAXI data with unprecedented orbital coverage for many orbits continuously, we have found a strong orbital dependence of the absorption column density and equivalent width of the iron emission line. A very large equivalent width of the iron line along with a small value of the column density in the orbital phase range 0.10-0.30 after the periastron passage indicates the presence of high density absorbing matter behind the neutron star in this orbital phase range. A low energy excess is also found in the spectrum at orbital phases around the pre-periastron X-ray flare. The orbital dependence of these parameters are then used to examine the various models about mode of accretion on to the neutron star in GX 301-2.

Magnetism and superconductivity in Sb-doped binary and ternary iron chalcogenide single crystals

We report the single crystal growth of antimony doped Fe1+yTe and Fe1+yTe0.5Se0.5 (Fe1+ySbxTe1-x (x=0, 2%, 5%) and Fe1+yTe0.49Se0.49Sb0.02) by a modified horizontal Bridgman method. Growth parameters are optimized to obtain high quality single crystals. The antiferromagnetic (AFM) transition at T-N = 62.2 K which is a first order transition, shifts to lower temperature on doping in Fe1+yTe. Alternately when the chalcogen site of the ternary compound Fe1+yTe0.5Se0.5 is doped with Sb, superconductivity is preserved albeit the superconducting transition temperature (T-C) falls slightly and a concomitant reduction occurs in superconducting volume fraction. (C) 2013 Elsevier B.V. All rights reserved,

Phonon anomalies, orbital-ordering and electronic raman scattering in iron-pnictide Ca(Fe0.97Co0.03)(2)As-2: temperature-dependent Raman study

We report inelastic light scattering studies on Ca(Fe0.97Co0.03)(2)As-2 in a wide spectral range of 120-5200 cm(-1) from 5 to 300 K, covering the tetragonal to orthorhombic structural transition as well as magnetic transition at T-sm similar to 160 K. The mode frequencies of two first-order Raman modes B-1g and E-g, both involving the displacement of Fe atoms, show a sharp increase below T-sm. Concomitantly, the linewidths of all the first-order Raman modes show anomalous broadening below T-sm, attributed to strong spin-phonon coupling. The high frequency modes observed between 400 and 1200 cm(-1) are attributed to electronic Raman scattering involving the crystal field levels of d-orbitals of Fe2+. The splitting between xz and yz d-orbital levels is shown to be similar to 25 meV, which increases as temperature decreases below T-sm. A broad Raman band observed at similar to 3200 cm(-1) is assigned to two-magnon excitation of the itinerant Fe 3d antiferromagnet.

Hydrogen bonding, halogen bonding and lithium bonding: an atoms in molecules and natural bond orbital perspective towards conservation of total bond order, inter- and intra-molecular bonding

One hundred complexes have been investigated exhibiting D-X center dot center dot center dot A interactions, where X = H, Cl or Li and DX is the `X bond' donor and A is the acceptor. The optimized structures of all these complexes have been used to propose a generalized `Legon-Millen rule' for the angular geometry in all these interactions. A detailed Atoms in Molecules (AIM) theoretical analysis confirms an important conclusion, known in the literature: there is a strong correlation between the electron density at the X center dot center dot center dot A bond critical point (BCP) and the interaction energy for all these interactions. In addition, we show that extrapolation of the fitted line leads to the ionic bond for Li-bonding (electrostatic) while for hydrogen and chlorine bonding, it leads to the covalent bond. Further, we observe a strong correlation between the change in electron density at the D-X BCP and that at the X center dot center dot center dot A BCP, suggesting conservation of the bond order. The correlation found between penetration and electron density at BCP can be very useful for crystal structure analysis, which relies on arbitrary van der Waals radii for estimating penetration. Various criteria proposed for shared-and closed-shell interactions based on electron density topology have been tested for H/Cl/Li bonded complexes. Finally, using the natural bond orbital (NBO) analysis it is shown that the D-X bond weakens upon X bond formation, whether it is ionic (DLi) or covalent (DH/DCl) and the respective indices such as ionicity or covalent bond order decrease. Clearly, one can think of conservation of bond order that includes ionic and covalent contributions to both D-X and X center dot center dot center dot A bonds, for not only X = H/Cl/Li investigated here but also any atom involved in intermolecular bonding.

An encaged sigma* orbital in 3-methoxy-2,4,10-trioxaadamantane. Preferred exo-anomeric effect as revealed by the crystal structure

In the titled tricyclic orthocarbonate derivative, the three endocyclic C-O bonds are longer than the exo-cyclic C-O bond (similar to 4.40 angstrom vs. similar to 1.37 angstrom). This indicates an anomeric-type interaction between the two electron lone pairs on the exocyclic oxygen atom and the antibonding orbitals of the two antiperiplanar endocyclic C-O bonds. The remaining endocyclic C-O bond - marginally shorter than the other two apparently adds to this effect. Intriguingly, the antibonding orbital of the exocyclic C-O bond extends into the interior of the adamantyl cage, and is stereoelectronically prevented from overlapping with any of the six adjacent lone pairs. The results also seem to indicate a preference for interaction between a single donor oxygen atom and multiple acceptor antibonding orbitals rather than vice versa. The results add insightfully to the substantial body of evidence favouring the antiperiplanar lone pair hypothesis (ALPH). (C) 2014 Elsevier B.V. All rights reserved.

The Self-Association of Graphane Is Driven by London Dispersion and Enhanced Orbital Interactions

We investigated the nature of the cohesive energy between graphane sheets via multiple CH center dot center dot center dot HC interactions, using density functional theory (DFT) including dispersion correction (Grimmes D3 approach) computations of n]graphane sigma dimers (n = 6-73). For comparison, we also evaluated the binding between graphene sheets that display prototypical pi/pi interactions. The results were analyzed using the block-localized wave function (BLW) method, which is a variant of ab initio valence bond (VB) theory. BLW interprets the intermolecular interactions in terms of frozen interaction energy (Delta E-F) composed of electrostatic and Pauli repulsion interactions, polarization (Delta E-pol), charge-transfer interaction (Delta E-CT), and dispersion effects (Delta E-disp). The BLW analysis reveals that the cohesive energy between graphane sheets is dominated by two stabilizing effects, namely intermolecular London dispersion and two-way charge transfer energy due to the sigma CH -> sigma*(HC) interactions. The shift of the electron density around the nonpolar covalent C-H bonds involved in the intermolecular interaction decreases the C-H bond lengths uniformly by 0.001 angstrom. The Delta E-CT term, which accounts for similar to 15% of the total binding energy, results in the accumulation of electron density in the interface area between two layers. This accumulated electron density thus acts as an electronic glue for the graphane layers and constitutes an important driving force in the self-association and stability of graphane under ambient conditions. Similarly, the double faced adhesive tape style of charge transfer interactions was also observed among graphene sheets in which it accounts for similar to 18% of the total binding energy. The binding energy between graphane sheets is additive and can be expressed as a sum of CH center dot center dot center dot HC interactions, or as a function of the number of C-H bonds.

Evaluation of Precipitation Retrievals From Orbital Data Products of TRMM Over a Subtropical Basin in India

The spatial error structure of daily precipitation derived from the latest version 7 (v7) tropical rainfall measuring mission (TRMM) level 2 data products are studied through comparison with the Asian precipitation highly resolved observational data integration toward evaluation of the water resources (APHRODITE) data over a subtropical region of the Indian subcontinent for the seasonal rainfall over 6 years from June 2002 to September 2007. The data products examined include v7 data from the TRMM radiometer Microwave Imager (TMI) and radar precipitation radar (PR), namely, 2A12, 2A25, and 2B31 (combined data from PR and TMI). The spatial distribution of uncertainty from these data products were quantified based on performance metrics derived from the contingency table. For the seasonal daily precipitation over a subtropical basin in India, the data product of 2A12 showed greater skill in detecting and quantifying the volume of rainfall when compared with the 2A25 and 2B31 data products. Error characterization using various error models revealed that random errors from multiplicative error models were homoscedastic and that they better represented rainfall estimates from 2A12 algorithm. Error decomposition techniques performed to disentangle systematic and random errors verify that the multiplicative error model representing rainfall from 2A12 algorithm successfully estimated a greater percentage of systematic error than 2A25 or 2B31 algorithms. Results verify that although the radiometer derived 2A12 rainfall data is known to suffer from many sources of uncertainties, spatial analysis over the case study region of India testifies that the 2A12 rainfall estimates are in a very good agreement with the reference estimates for the data period considered.