Relaxor ferroelectric-like glassy dielectric dispersion in the triple perovskite Ba3CoSb2O9.

In this work, the dielectric response of polycrystalline Ba3CoSb2O9 was studied as a function of temperature (30 to 900 °C) and frequency (10 Hz to 10 MHz). The triple perovskite Ba3CoSb2O9 was successfully synthesized and characterized for structural and dielectric properties. The Rietveld analysis of the X-ray diffractogram confirms the formation of a hexagonal phase with P63/mmc symmetry. This centrosymmetric 3(BaCo1/3Sb2/3O3) perovskite shows structural similarity to a prototypical non-centrosymmetric relaxor ferroelectric, PbMg1/3Nb2/3O3. The dielectric constant, ε', follows a non-Debye Cole-Cole relation and exhibits anomalous responses such as: (a) a thermally activated colossal dielectric constant (>105) and (b) a highly dispersive peak maximum (523-853 K). The real part of ac conductivity, σ', also shows a change of approximately 6 orders in magnitude (10-8 to 10-2 S m-1). Validation of Jonscher's law and impedance (Nyquist plot) and modulus (M'') analyses indicate that hopping polarization is the predominant thermally activated mechanism. Moreover, the large value of ε' and its dispersion were found to be highly correlated with the underlying crystal structure and were attributed to the local ionic site ordering. The study suggests that the anomalous dielectric dispersion must have an intrinsic origin.

Spin-Orbit Excitons in a Correlated Metal: Raman Scattering Study of Sr_{2}RhO_{4}.

Using Raman spectroscopy to study the correlated 4d-electron metal Sr_{2}RhO_{4}, we observe pronounced excitations at 220 meV and 240 meV with A_{1g} and B_{1g} symmetries, respectively. We identify them as transitions between the spin-orbit multiplets of the Rh ions, in close analogy to the spin-orbit excitons in the Mott insulators Sr_{2}IrO_{4} and α-RuCl_{3}. This observation provides direct evidence for the unquenched spin-orbit coupling in Sr_{2}RhO_{4}. A quantitative analysis of the data reveals that the tetragonal crystal field Δ in Sr_{2}RhO_{4} has a sign opposite to that in insulating Sr_{2}IrO_{4}, which enhances the planar xy orbital character of the effective J=1/2 wave function. This supports a metallic ground state, and suggests that c-axis compression of Sr_{2}RhO_{4} may transform it into a quasi-two-dimensional antiferromagnetic insulator.

Spin reorientation transition and spin dynamics study of perovskite orthoferrite TmFeO3 detected by electron paramagnetic resonance.

The temperature-dependent spin-reorientation transition (SRT) and spin interaction mechanism of bulk TmFeO3 were studied by the electron paramagnetic resonance (EPR) method. The combined experimental results of magnetic curves and EPR spectra confirmed that there is an antiferromagnetic transition at 85 K with a reentering ferromagnetic state due to the spin-reorientation behavior. In the high-temperature region of T > 90 K, there are three distinct resonance peaks in the EPR spectrum, which indicates the presence of multiple magnetic phases (canted antiferromagnetic, weak ferromagnetic, and paramagnetic phases). In the low-temperature region (T < 85 K), the temperature dependence of the EPR linewidth, effective g-factor, and intensity can be used to infer a strong spin-lattice correlation. Different magnetic interactions such as Fe3+-Fe3+, Fe3+-Tm3+, and Tm3+-Tm3+ lead to a paramagnetic-canted antiferromagnetic phase at T > 85 K, with SRT between 85-65 K and ferromagnetic interaction at the lower temperature, respectively. Above 90 K, we find that the spin relaxation mechanism is determined by the mixture of spin-spin and spin-lattice interactions. Below 85 K, the transverse relaxation rate increases with the decrease in temperature, which is consistent with the weakening of the fluctuating internal field in this temperature region. This EPR detection provides a new method to clarify the strong spin coupling in antiferromagnetic materials.

Spin-lattice correlation in Eu3+ doped antiferromagnet TmFeO3.

We report the physical properties of Eu-doped bulk TmFeO3 through X-ray diffraction, magnetic susceptibility (χ), Raman scattering and X-ray absorption spectroscopy (XAS) study, which shows a similar orthorhombic structure with the Pbnm space group as TmFeO3. Magnetic measurement on Eu-doped TmFeO3 provides evidence for spin reorientations of Fe3+. Further, the Raman spectra of Eu3+ doped TmFeO3 show significant changes in Raman modes as a function of temperature, which are evidence for strong spin-lattice interaction. From the XAS spectra, the L-edge of Fe provides information on the valence state of Fe, whereas the K-edge of oxygen shows that the compound has a strong influence on the hybridization of the O(2p) state with the 3d states of Fe.

Magnetic Exchange Interaction in Nitronyl Nitroxide Radical-Based Single Crystals of 3d Metal Complexes: A Combined Experimental and Theoretical Study.

Two stable nitronyl nitroxide free radicals {R 1 = 4'-methoxy-phenyl-4,4,5,5,-tetramethylimidazoline-1-oxyl-3-oxide (NNPhOMe) and R 2 = 2-(2'-thienyl)-4,4,5,5-tetramethylimidazoline 3-oxide 1-oxyl (NNT)} are successfully synthesized using Ullmann condensation. The reactions of these two radicals with 3d transition metal ions, in the form of M(hfac)2 (where M = Co or Mn, hfac: hexafluoroacetylacetone), result in four metal-organic complexes Co(hfac)2(NNPhOMe)2, 1; Co(hfac)2(NNT)2·(H2O), 2; Mn(hfac)2(NNPhOMe)·x(C7H16), 3; and Mn(hfac)2(NNT)2, 4. The crystal structure and magnetic properties of these complexes are investigated by single-crystal X-ray diffraction, dc magnetization, infrared, and electron paramagnetic resonance spectroscopies. The compounds 1 and 4 crystallize in the triclinic, P1̅, space group, whereas complex 3 crystallizes in the monoclinic structure with the C2/c space group and forms chain-like structure along the c direction. The complex 2 crystallizes in the monoclinic symmetry with the P21/c space group in which the N-O unit of the radical coordinates with the Co ion through hydrogen bonding of a water molecule. All compounds exhibit antiferromagnetic interactions between the transition metal ions and nitronyl nitroxide radicals. The magnetic exchange interactions (J/K B) are derived using isotropic spin Hamiltonian H = -2J∑(S metal S radical) for the model fitting to the magnetic susceptibility data for 1, 2, 3, and 4. The exchange interaction strengths are found to be -328, -1.25, -248, and -256 K, for the 1, 2, 3, and 4 metal-organic complexes, respectively. Quantum chemical density functional theory (DFT) computations are carried out on several models of the metal-radical complexes to elucidate the magnetic interactions at the molecular level. The calculations show that a small part of the inorganic spins are delocalized over the oxygens from hfac {∼0.03 for Co(II) and ∼0.015 for Mn(II)}, whereas a more significant fraction {∼0.24 for Mn(II) and ∼0.13 for Co(II)} of delocalized spins from the metal ion is transferred to the coordinated oxygen atom(s) of nitronyl nitroxide.

Magnetic properties of manganese based one-dimensional spin chains.

We have correlated the structure-property relationship of three manganese-based inorganic-organic hybrid structures. Compound 1, [Mn2(OH-BDC)2(DMF)3] (where BDC = 1,4-benzene dicarboxylic acid and DMF = N,N'-dimethylformamide), contains Mn2O11 dimers as secondary building units (SBUs), which are connected by carboxylate anions forming Mn-O-C-O-Mn chains. Compound 2, [Mn2(BDC)2(DMF)2], contains Mn4O20 clusters as SBUs, which also form Mn-O-C-O-Mn chains. In compound 3, [Mn3(BDC)3(DEF)2] (where DEF = N,N'-diethylformamide), the distorted MnO6 octahedra are linked to form a one-dimensional chain with Mn-O-Mn connectivity. The magnetic properties were investigated by means of magnetization and heat capacity measurements. The temperature dependent magnetic susceptibility of all the three compounds could be nicely fitted using a one-dimensional S = 5/2 Heisenberg antiferromagnetic chain model and the value of intra-chain exchange coupling (J/k(B)) between Mn(2+) ions was estimated to be ∼1.1 K, ∼0.7 K, and ∼0.46 K for compounds 1, 2, and 3, respectively. Compound 1 does not undergo any magnetic long-range-order down to 2 K while compounds 2 and 3 undergo long-range magnetic order at T(N) ≈ 4.2 K and ≈4.3 K, respectively, which are of spin-glass type. From the values of J/k(B) and T(N) the inter-chain coupling (J(⊥)/k(B)) was calculated to be about 0.1J/k(B) for both compounds 2 and 3, respectively.