Magnetic interactions in the oxide systems LaNi1-xMxO3 (M = Cr, Fe, or Co)

Magnetic susceptibilities of several members of the series of oxides of the general formula LaNi1-xMxO3 (M = Cr, Fe, or Co) are reported. The oxides show evidence for interesting ferrimagnetic (Cr and Co) and antiferromagnetic (Fe) interactions.

Unusual effects of anisotropic bonding in Cu(II) and Ni(II) oxides with K2NiF4 structure

Geometric constraints present in A2BO4 compounds with the tetragonal-T structure of K2NiF4 impose a strong pressure on the B---OII---B bonds and a stretching of the A---OI---A bonds in the basal planes if the tolerance factor is t congruent with RAO/√2 RBO < 1, where RAO and RBO are the sums of the A---O and B---O ionic radii. The tetragonal-T phase of La2NiO4 becomes monoclinic for Pr2NiO4, orthorhombic for La2CuO4, and tetragonal-T′ for Pr2CuO4. The atomic displacements in these distorted phases are discussed and rationalized in terms of the chemistry of the various compounds. The strong pressure on the B---OII---B bonds produces itinerant σ*x2−y2 bands and a relative stabilization of localized dz2 orbitals. Magnetic susceptibility and transport data reveal an intersection of the Fermi energy with the d2z2 levels for half the copper ions in La2CuO4; this intersection is responsible for an intrinsic localized moment associated with a configuration fluctuation; below 200 K the localized moment smoothly vanishes with decreasing temperature as the d2z2 level becomes filled. In La2NiO4, the localized moments for half-filled dz2 orbitals induce strong correlations among the σ*x2−y2 electrons above Td reverse similar, equals 200 K; at lower temperatures the σ*x2−y2 electrons appear to contribute nothing to the magnetic susceptibility, which obeys a Curie-Weiss law giving a μeff corresponding to S = 1/2, but shows no magnetic order to lowest temperatures. These surprising results are verified by comparison with the mixed systems La2Ni1−xCuxO4 and La2−2xSr2xNi1−xTixO4. The onset of a charge-density wave below 200 K is proposed for both La2CuO4 and La2NiO4, but the atomic displacements would be short-range cooperative in mixed systems. The semiconductor-metallic transitions observed in several systems are found in many cases to obey the relation Ea reverse similar, equals kTmin, where varrho = varrho0exp(−Ea/kT) and Tmin is the temperature of minimum resistivity varrho. This relation is interpreted in terms of a diffusive charge-carrier mobility with Ea reverse similar, equals ΔHm reverse similar, equals kT at T = Tmin.

Preparation, IR and nuclear magnetic resonance studies on the rare-earth perchlorate complexes of 3-methylpyridine-1-oxide

THE COMPLEXES of pyridine-l-oxide and 2- and 4-substituted pyridine-l-oxides have been investigated previously[l]. The complexes of 3-substituted pyfidine-l-oxides, however, have received little attention. The rare-earth complexes of pyridine-Ioxide[l, 2], 4-methylpyridine- l-oxide [1] and 2,6- dimethylpyfidine-l-oxide[3,4] have been reported earlier. The present paper deals with the isolation and characterisation of 3-methylpyridine-l-oxide (3-Picoline-N-oxide, 3-PicNO) complexes with rare-earth perchlorates.

Long-range Coulomb interactions and nanoscale electronic inhomogeneities in correlated oxides

Electronic, magnetic, or structural inhomogeneities ranging in size from nanoscopic to mesoscopic scales seem endemic and are possibly generic to colossal magnetoresistance manganites and other transition metal oxides. They are hence of great current interest and understanding them is of fundamental importance. We show here that an extension, to include long-range Coulomb interactions, of a quantum two-fluid l-b model proposed recently for manganites [Phys. Rev. Lett. 92, 157203 (2004)] leads to an excellent description of such inhomogeneities. In the l-b model two very different kinds of electronic states, one localized and polaronic (l) and the other extended or broad band (b) coexist. For model parameters appropriate to manganites and even within a simple dynamical mean-field theory (DMFT) framework, it describes many of the unusual phenomena seen in manganites, including colossal magnetoresistance (CMR), qualitatively and quantitatively. However, in the absence of long-ranged Coulomb interaction, a system described by such a model would actually phase separate, into macroscopic regions of l and b electrons, respectively. As we show in this paper, in the presence of Coulomb interactions, the macroscopic phase separation gets suppressed and instead nanometer scale regions of polarons interspersed with band electron puddles appear, constituting a kind of quantum Coulomb glass. We characterize the size scales and distribution of the inhomogeneity using computer simulations. For realistic values of the long-range Coulomb interaction parameter V-0, our results for the thresholds for occupancy of the b states are in agreement with, and hence support, the earlier approach mentioned above based on a configuration averaged DMFT treatment which neglects V-0; but the present work has features that cannot be addressed in the DMFT framework. Our work points to an interplay of strong correlations, long-range Coulomb interaction, and dopant ion disorder, all inevitably present in transition metal oxides as the origin of nanoscale inhomogeneities rather than disorder frustrated phase competition as is generally believed. As regards manganites, it argues against explanations for CMR based on disorder frustrated phase separation and for an intrinsic origin of CMR. Based on this, we argue that the observed micrometer (meso) scale inhomogeneities owe their existence to extrinsic causes, e.g., strain due to cracks and defects. We suggest possible experiments to validate our speculation.

R3Mn1.5CuV0.5O9 (R = Y, Ho, Er, Tm, Yb and Lu) and Lu3Mn3-3xCu2xVxO9: New noncentro symmetric oxides related to YMnO3

We report formation of new noncentrosymmetric oxides of the formula, R3Mn1.5CuV0.5O9 for R = Y, Ho, Er, Tm, Yb and Lu, possessing the hexagonal RMnO3 (space group P6(3)cm) structure. These oxides could be regarded as the x = 0.5 members of a general series R3Mn3-3xCu2xVxO9. Investigation of the Lu-Mn-Cu-V-O system reveals the existence of isostructural solid solution series, Lu3Mn3-3xCu2xVxO9 for 0 < x <= 0.75. Magnetic and dielectric properties of the oxides are consistent with a random distribution of Mn3+, Cu2+ and V5+ atoms that preserve the noncentrosymmetric RMnO3 structure. (c) 2006 Elsevier Ltd. All rights reserved.

Suppression of spinel formation to induce reversible thermal behavior in the layered double hydroxides (LDHs) of Co with Al, Fe, Ga, and In

The layered double hydroxides (LDHs) of Co with trivalent cations decompose irreversibly to yield oxides with the spinel structure. Spinel formation is aided by the oxidation of Co(II) to Co(III) in the ambient atmosphere. When the decomposition is carried out under N-2, the oxidation of Co(II) is suppressed, and the resulting oxide has the rock salt structure. Thus, the Co-Al-CO32-/Cl- LDHs yield oxides of the type Co1- Al-x(2x/3)rectangle O-x/3, which are highly metastable, given the large defect concentration. This defect oxide rapidly reverts back to the original hydroxide on soaking in a Na2CO3 solution. Interlayer NO3- anions, on the other hand, decompose generating a highly oxidizing atmosphere, whereby the Co-Al-NO3- LDH decomposes to form the spinel phase even in a N-2 atmosphere. The oxide with the defect rock salt structure formed by the thermal decomposition of the Co-Fe-CO32- LDH under N2, on soaking in a Na2CO3 solution, follows a different kinetic pathway and undergoes a solution transformation into the inverse spinel Co(Co, Fe)(2)O-4. Fe3+ has a low octahedral crystal field stabilization energy and therefore prefers the tetrahedral coordination offered by the structure of the inverse spinel rather than the octahedral coordination of the parent LDH. Similar considerations do not hold in the case of Ga- and In-containing LDHs, given the considerable barriers to the diffusion of M3+ (M=Ga, In) from octahedral to tetrahedral sites owing to their large size. Consequently, the In-containing oxide residue reverts back to the parent hydroxide, whereas this reconstruction is partial in the case of the Ga-containing oxide. These studies show that the reversible thermal behavior offers a competing kinetic pathway to spinel formation. Suppression of the latter induces the reversible behavior in an LDH that otherwise decomposes irreversibly to the spinel.

Electronic phase separation in correlated oxides: The phenomenon, its present status and future prospects

Many transition metal oxide materials of high chemical purity are not necessarily monophasic. Thus, single crystals of chemically pure rare earth manganites and cobaltates of the general formula Ln1-xAxMO3 (Ln=rare earth metal, A=alkaline earth metal, M=Mn, Co) exhibit the phenomenon of electronic phase separation wherein phases of different electronic and magnetic properties coexist. Such phase separation, the length scale of which can vary anywhere between a few nanometers to microns, gives distinct signatures in X-ray and neutron diffraction patterns, electrical and magnetic properties, as well as in NMR and other spectroscopies. While the probe one employs to investigate electronic phase separation depends on the length scale, it is noteworthy that direct imaging of the inhomogeneities has been accomplished. Some understanding of this phenomenon has been possible on the basis of some of the theoretical models, but we are far from unraveling the varied aspects of this new phenomenon. Herein, we present the highlights of experimental techniques and theoretical approaches, and comment on the future outlook for this fascinating phenomenon

Magnetization and magnetoresistive response of LiMn2O4 near the charge ordering transition

We report magnetization and magnetoresistance studies of the geometrically frustrated spinel compound LiMn2O4 near its charge ordering temperature. The effect of a 7 T magnetic field is to very slightly shift the transition in the resistivity to lower temperatures resulting in large negative magnetoresistance with significant hysteresis. This hysteresis is not reflected in the magnetization. These observations are compared with what is found in the colossal magnetoresistance and charge ordering perovskite manganese oxides. The manner in which geometric frustration influences the coupling of charge and spin degrees of freedom is examined.

Manganese-mediated ferromagnetism in La2Fe1-xMn2xCr1-xO6 perovskite oxides

We have investigated the structure and magnetic properties of the perovskite oxides of the formula La2Fe1-xMn2xCr1-xO6 (0 < x < 1.0). For 0 < x <= 0.5, the members adopt the orthorhombic (Pbnm) structure, where the transition metal atoms are disordered at the 4b sites and the MO6 (M = Fe, Mn, Cr) octahedra become increasingly distorted with increasing x. For 0.65 <= x < 1.0, the members adopt the rhombohedral (R-3c) structure that is similar to LaMnO3+delta (delta >= 0.1) where the MO6 octahedra are undistorted. While the magnetic properties of the latter series are largely similar to the parent LaMnO3+delta arising from the double-exchange (DE) between mixed valent Mn-III/Mn-IV, the magnetic properties of the orthorhombic members show a distinct (albeit weak) ferromagnetism (T-C similar to 200 K) that seems to arise from a Mn-III-mediated superexchange (SE) between Fe-III/Cr-III in the disordered perovskite structure containing Fe-III, Mn-III and Cr-III.

Synthesis, structure and magnetic properties of the polyoxovanadate cluster Zn-2(NH2(CH2)(2)NH2)(5)]{Zn(NH2(CH2)(2)NH2)(2)}(2){V18O42(H2O)\ ]center dot xH(2)O (x similar to 12), possessing a layered structure

A hydrothermal reaction of a mixture of ZnCl2, V2O5, ethylenediamine and water gave rise to a layered poly oxovanadate material. clusters. These clusters, with all the vanadium ions in the +4 state, are connected together through Zn(NH2(CH2)(2)NH2)(2) linkers forming a two-dimensional structure. The layers are also separated by distorted trigonal bipyramidal [Zn-2(NH2(CH2)(2)NH2)(5)] complexes. The Structure, thus, presents a dual role for the Zn-ethylenediamine complex. The magnetic susceptibility studies indicate that the interactions between the V centres in I are predominantly antiferromagnetic in nature and the compound shows highly frustrated behaviour. The magnetic properties are compared to the theoretical calculations based oil the Heisenberg model, in addition to correlating to the structure. Crystal data for the complexes are presented.

Electron paramagnetic resonance studies of some ternary oxides of copper (II)

The electron paramagnetic resonance (EPR) of ternary oxides of Cu(II) has been studied between 4.2 and 300 K. The systems include those with 180 degrees Cu-O-Cu interactions (such as Ln2CuO4, Sr2CuO2Cl2, Sr2CuO3 and Ca2CuO3) or 90 degrees Cu-O-Cu interactions (such as Y2Cu2O5 or BaCuO2) as well as those in which the Cu2+ ions are isolated (such as Y2BaCuO5, La1.8Ba1.2Cu0.9O4.8 and Bi2CuO4). The change in the EPR susceptibility as a function of temperature is compared with that of the DC magnetic susceptibility. Compounds with extended 180 degrees Cu-O-Cu interactions which have a low susceptibility also do not give EPR signals below room temperature. For compounds such as Ca2CuO3 with one-dimensional 180 degrees Cu-O-Cu interactions a weak EPR signal is found the temperature dependence of which is very different from that of the DC susceptibility. For Y2BaCuO5 as well as for La1.8Ba1.2Cu0.9O4.8 the EPR susceptibility as well as its temperature variation are comparable with those of the static susceptibility near room temperature but very different at low temperatures. Bi2CuO4 also shows a similar behaviour. In contrast, for Y2Cu2O5, in which the copper ions have a very distorted nonsquare-planar configuration, the EPR and the static susceptibility show very similar temperature dependences. In general, compounds in which the copper ions have a square-planar geometry give no EPR signal in the ground state (0 K) while those with a distortion from square-planar geometry do give a signal. The results are analysed in the light of recent MS Xalpha calculations on CuO46- square-planar clusters with various Cu-O distances as well as distortions. It is suggested that in square-planar geometry the ground state has an unpaired electron in anionic orbitals which is EPR inactive. Competing interactions from other cations, an increase in Cu-O distance or distortions from square-planar geometry stabilise another state which has considerably more Cu 3d character. These states are EPR active. Both these states, however, are magnetic. For isolated CuO46- clusters the magnetic interactions seem to involve only the states which have mainly anionic character.

Wire-cylinder corona discharge with the wire at positive potential studies of iron oxides

A wire-cylinder corona discharge was studied in nitrogen and dry air in crossed electric and magnetic fields for values of magnetic field ranging from 0 to 3000 G with the wire at positive potential. In the absence of a magnetic field pre-onset streamers and pulses were observed in nitrogen. In both nitrogen and dry air breakdown streamers were observed just before spark breakdown of the gap. Furthermore, experiments in dry air at atmospheric pressure in an electric field indicate regular pre-onset streamers appearing at time intervals of 19.5 µs. The appearance of regular pre-onset streamers suggests that it is not possible for negative ions to form a sheath close to the anode as postulated by Hermstein (1960) for the formation of steady or glow corona in a point-plane gap.

A study of cubic bismuth oxides of the type bi(26-X)m(X)O(40-delta) (m=ti, mn, fe, co, ni or pb) related to gamma-bi2O3

A structural investigation of cubic oxides (space group I23) of the formula Bi(26-x)M(x)O(40-delta) (M = Ti, Mn, Fe, Co, Ni and Pb) related to the Y-Bi2O3 phase has been carried out by the Rietveld profile analysis of high-resolution X-ray powder diffraction data in order to establish the cation distributions. Compositional dependence of the cation distribution has been examined in the case of Bi26-xCoxO40-delta (1 < x < 16). The study reveals that in Bi(26-X)M(X)O(40-delta) with M = Ti, Mn, Fe, Co or Pb, the M cations tend to occupy tetrahedral (2a) sites when x < 2 while the octahedral (24f) sites are shared by the excess Co or Ni cations with Bi atoms when x > 2. Also experimental magnetic moments of Mn, Co and Ni derivatives have been used to establish the valence state and distribution of these cations.

Wet chemical syntheses of ultrafine multicomponent ceramic powders through gel to crystallite conversion

Coarse (BOn/2)-O-n+/xH(2)O (10oxides (A=Ba, Sr, Ca, Mg or Pb; B=Zr, Ti, Sn, Fe, Al or Cr). These include ABO, perovskites and their solid solutions, polytitanates, hexaferrites and related phases, aluminates with spinel or tridymite structure and chromates. The nanosized crystallites are often in metastable phases, such as cubic BaTiO3 at room temperature or superparamagnetic hexaferrites. Through the same route, luminescent phosphors of aluminates doped with rare-earth metals could be prepared. The present results indicate the general features of the gel-crystallite (G-C) conversion involving the instability of the metal hydroxide gel brought about by the disruption of the ionic pressure in the gel as a result of the faster diffusion of A(2+) ions through the solvent cavities within the gel frame work. This is accompanied by the splitting of the bridging groups like B-(OH)-B or B-O-B, leading to the breakdown of the gel into crystallites. G-C conversion has advantages as a method of synthesis of ceramics in terms of operational cost and procedural simplicity.

Giant magnetoresistance in lanthanum strontium yttrium manganese oxides (La(1-x)Sr(x-z)YuMnO(3))

Electron transport and magnetic properties of several compositions of the La1-xSx-zYzMnO3 system have been investigated in order to explore the effect of yttrium substitution on the magnetoresistance and related properties of these manganates. Yttrium substitution lowers the T-c and the insulator-metal transition temperature, while increasing the peak resistivity. A comparison of the properties of La1-xSrx-zYzMnO3 with the corresponding La1-xCax-zYzMnO3 compositions shows that the observed properties can be related to the average size of the A-site cations.