Crystal field effect and geometric frustration in Er2Ti2O7 —an XY antiferromagnetic pyrochlore

Magnetic susceptibility of powder Er₂Ti₂O₇ (ErT) is measured between 300 K and 80 K. shows a Curie-Weiss (CW) type behaviour with   ErTiO_3.5 and . A crystal field (CF) analysis of our experimental data, g-values (g_∥=0.27 and g_⊥=7.8) and the positions of two CF levels (reported earlier from an inelastic neutron scattering study) provide CF parameters and CF levels of the ground ⁴I_15/2 and excited multiplets of ErT. The theoretical follows a CW-type behaviour, with . Single-ion magnetic anisotropy (χ_⊥−χ_∥) is 9500×10⁻⁶ emu/mol ErTiO_3.5 at 300 K, which increases by ∼54 times at 10 K and ErT resembles an XY planar system. It can be inferred from CF analysis that the earlier observed change of from −13 K to −22 K below 50 K is not due to the CF effect. Nuclear hyperfine (HF) levels of ¹⁶⁷ErT and ¹⁶⁶ErT are calculated and the theoretical curve of vs. T (K) for T<T_N matches the observed results. Mössbauer lines expected for ¹⁶⁶ErT are also predicted.     

Field suppression of the modulated phase of Ce2Pd2Sn

Low temperature magnetic (M) and thermal (C_P) properties of the intermetallic compound Ce₂Pd₂Sn have been investigated at zero and different magnetic fields. Two transitions were recognized at and , with latter nearly coinciding with the extrapolated Curie-Weiss temperature . The Curie factor evaluated from T≥T_M, is ≈2μ_B. The positive value of θ_P, the triangular coordination of the magnetic (Ce) atoms and the weak effect of applied magnetic field, reveal that T_M cannot be considered as a canonic antiferromagnetic transition like claimed in the literature. M(T) measurements under moderate magnetic fields () show T_C(B) increasing while T_M(B) is practically not affected. Both transition merge in a critical point at for , where the intermediate phase is suppressed. At , the cusp of a first order transition is observed in C_P(T). According to the proposed ferromagnetic ground state, it is followed by a C_P(T)∝T^3/2exp(-E_g/T) dependence, with a gap of anisotropy .     

Low-temperature measurements of magnetic susceptibility and specific heat of Eu2Ti2O7—An XY pyrochlore

Magnetic susceptibility obtained from magnetization measurement (for fields H=0.1 and 1.0 T) of polycrystalline Eu₂Ti₂O₇ shows two distinct features. Firstly, increases on cooling below 300 K and attains a temperature-independent constant value at 68 K (T_max). Secondly, shows an antiferromagnetic increase below 4.9±0.1 K. The former behavior is explained by crystal field (CF) theory. CF levels and wave functions of ground and excited states are determined accurately from analyses of and earlier reported Mössbauer and optical spectra. Analysis of vs. 1/T curve at low temperatures gives the classical nearest-neighbor exchange interaction J^cl=−0.76 K and a weak dipolar interaction D_nn=0.0056 K. C_P of polycrystalline sample of Eu₂Ti₂O₇ and Y₂Ti₂O₇ are measured between 1.8-35 and 1.8-120 K respectively and θ_D vs. T (K) curves are calculated. At 4 K, θ_D of Eu₂Ti₂O₇ shows a kink and dC_P/dT curve show a maximum. Optical results show energy exchange between Eu³⁺ ions at intrinsic and extrinsic (defect) sites via super-exchange interaction at low temperature which may account for the observed anomalous behavior of and C_P.     

4-benzyl pyridinium dihydrogenmonophosphate C6H5CH2C5H4NHH2PO4 : Single-crystal structure and its conductivity in polycrystalline form

The salt 4-benzyl pyridinium dihydrogenmonophosphate is monoclinic P2₁/c with the following unit cell dimensions: ; ; ; and β=97.328(11). Also, , D_x=1.403, , F(000)=560; ; and R=0.0495 and R_w=0.0964 for 3733 independent reflections. The structure consists of infinite parallel two-dimensional planes built of H₂PO₄⁻ anions and C₆H₅CH₂C₅H₄NH⁺ cations mutually connected by strong O-H ?O and N-H ?O hydrogen bonding. There are no contacts other than the normal Van der Waals interactions between the layers. The conductivity relaxation parameters associated with some H⁺ conduction have been determined from an analysis of the spectrum measured in a wide temperature range.     

Relaxor behavior of K0.5La0.5Bi2Ta2O9 ceramics

Potassium lanthanum bismuth tantalate (K_0.5La_0.5Bi₂Ta₂O₉), a new relaxor ferroelectric was synthesized via the solid-state reaction route. X-ray structural studies along with Rietveld refinement confirmed it to be an n=2 member of the Aurivillius family of oxides and the refined lattice parameters are , and . The appearance of 1/2{h00} and 1/2{hk0} type superlattice reflections in the electron diffraction patterns reflected the presence of ordered polar regions. A broad dielectric peak associated with frequency dependent dielectric maximum temperature was observed. The value of the diffuseness parameter γ=1.93, obtained from the fit of a modified Curie-Weiss law established the relaxor nature of the title compound. The dielectric relaxation obeyed the Vogel-Fulcher relation wherein and . The relaxor behavior was attributed to the local polar ordering on A-sites.     

Preparation-dependent properties of Ca(Cu,Mn)7O12 CMR materials

Both magnetic ordering temperatures and lattice constants were observed to be a function of preparation temperature for single-phase CaCuMn₆O₁₂ CMR ceramics of the same cation, oxygen composition and crystal structure. It was found for the first time that higher preparation temperatures result in a linear increase of a cubic cell parameter a, , and in a sharp decrease of magnetic ordering temperatures , by about , for quenched samples. High resolution NPD experiments have shown the presence of antisite defects resulting in partial occupation of octahedral (8c) sites by Cu²⁺ at higher preparation temperatures as never assumed for an ideal structure. The data obtained give a new insight to the problem of functional properties reproducibility suggesting stronger requirements for the production control of CMR materials.     

Effects of doping Na on the structure and physical properties of La2/3Ca1/3MnO3

Effects of doping Na on the structure, electrical and magnetic properties of La_2/3Ca_1/3MnO₃ are investigated. A structural phase transition from orthorhombic to rhombohedral structure takes place at y=0.375. All samples show metal-insulator (M-I) transition at the transition temperature and undergo the transition from paramagnetism to ferromagnetism at the Curie temperature T_C. and T_C increase monotonically with increasing Na content. However the Na-doped samples have a shoulder in their electrical transport curves found below and shows a widened magnetic transition process. On the other hand, intrinsic colossal magnetoresistance (CMR) peaks are observed in all the samples, but samples with y around 0.25 show two MR peaks which can be attributed to magnetic inhomogeneity induced by the doped Na⁺ ions. Here we propose a method to broaden the CMR peak of perovskite manganite, which is beneficial for practical applications.     

Molecular dynamics of [(CH2OH)3CNH3]2SiF6 by phase transition of 178 K

We have investigated the molecular motions of TRIS⁺ ([(CH₂OH)₃CNH₃]⁺) and ions in the [(CH₂OH)₃CNH₃]₂SiF₆ crystal below room temperature from the measurements of the spin-lattice relaxation time T₁ and the NMR absorption line of ¹H and ¹⁹F nuclei, in order to elucidate the changes of the molecular motions by the phase transition of T_c=178 K. The narrowing of the ¹⁹F-NMR line was observed around T_c=178 K and the reorientation of the anion appears above T_c. Moreover, from the analysis of the temperature dependence of T₁, we have observed that the activation energy of the reorientational motion of ions changes from 0.168 eV (T>T_c) to 0.185 eV (T<T_c). Based on these results, we found that the reorientational motion of ions is closely related to the origin of the phase transition at T_c. In addition, from the measurement of the ¹H-NMR line, we also found that the reorientational motion of H₂ in the -CH₂OH group becomes active accompanied by the phase transition.     

Charge and orbital ordering in Na0.5CoO2

The ground state of Na_0.5CoO₂ has been calculated using the full potential local orbital method and local density approximation plus Hubbard U (); the results demonstrate that charge and orbital ordering evidently exist in the present system in association with the antiferromagnetic state. Notable structural features observed between 300 and 30 K have been carefully examined using in situ TEM investigations, a superstructure with a wave vector of Q1=a^∗/2, becoming commonly visible below , can be interpreted as the charge/orbital ordering on the Co1 and Co2 sites. Moreover, we have also observed another notable superstructure with Q2=a^∗/4 below the phase transition of , which suggests a more complicated orbital ordered state existing at lower temperatures.     

Theoretical study of local lattice structure of Mn in perovskite fluorides A2MF4 (A=K, Rb; M=Mg, Zn, Cd) series

A theoretical method for investigating the inter-relation between the molecular structure and electronic structure has been established on the basis of the 252×252 complete energy matrices for a 3d⁵ configuration ion in a tetragonal ligand field. By means of this method, which is independent of the X-ray diffraction, the local structure of the paramagnetic Mn²⁺ ion in perovskite fluorides A₂MF₄ (A=K, Rb; M=Zn, Mg, Cd) are determined directly by analyzing the EPR spectrum of octahedral Mn²⁺ center in A₂MF₄ crystals and the optical absorption spectrum of the (MnF₆)⁴⁻ cluster. It is shown that, comparing with the octahedral cubic structure, the local micro-structure in the vicinity of Mn²⁺ displays an elongated distortion when and a compressed distortion when , and ΔR vs. as well as ΔR vs. in the distortion region is, respectively, approximately linear. Simultaneously, the theoretical zero-field-splitting parameters , and are in good agreement with the experimental values.