Interplay of lattice-spin-orbital coupling and Jahn-Teller effect in noncollinear spinel TixMn1-x(FeyCo1-y)2O4: a neutron diffraction study.

Local magnetostructural changes and dynamical spin fluctuations in doubly diluted spinel TixMn1‒x(FeyCo1‒y)2O4has been reported by means of neutron diffraction and magnetization studies. Two distinct sets of compositions (i)x(Ti) = 0.20 andy(Fe) = 0.18; (ii)x(Ti) = 0.40 andy(Fe) = 0.435 have been considered for this study. The first compound of equivalent stoichiometry Ti0.20Mn0.80Fe0.36Co1.64O4exhibits enhanced tetragonal distortion across the ferrimagnetic transition temperatureTC= 258 K in comparison to the end compound MnCo2O4(TC∼ 180 K) with a characteristic ratioct/√2atof 0.99795(8) demonstrating robust lattice-spin-orbital coupling. However, in the second case Ti0.40Mn0.60Fe0.87Co1.13O4with higherB-site compositions, the presence of Jahn-Teller ions with distinct behavior appears to counterbalance the strong tetragonal distortion thereby ceasing the lattice-spin-orbital coupling. Both the investigated systems show the coexistence of noncollinear antiferromagnetic and ferrimagnetic components in cubic and tetragonal settings. On the other hand, the dynamical ac-susceptibility,χac(T) reveals a cluster spin-glass state with Gabay-Toulouse (GT) like mixed phases behaviour belowTC. Such dispersive behaviour appears to be sensitive to the level of octahedral substitution. Further, the field dependence ofχac(T) follows the weak anisotropic GT-line behaviour with crossover exponent Φ lies in the range 1.38-1.52 on theH-Tplane which is in contrast to theB-site Ti substituted MnCo2O4spinel that appears to follow irreversible non-mean-field AT-line behaviour (Φ âˆ¼ 3 +δ). Finally, the Arrott plots analysis indicates the presence of a pseudo first-order like transition (T< 20 K) which is in consonance with and zero crossover of the magnetic entropy change within the frozen spin-glass regime.

Reentrant canonical spin-glass dynamics and tunable field-induced transitions in (GeMn)Co2O4Kagomé lattice.

We report on the reentrant canonical semi spin-glass characteristics and controllable field-induced transitions in distorted Kagomé symmetry of (GeMn)Co2O4. ThisB-site spinel exhibits complicated, yet interesting magnetic behaviour in which the longitudinal ferrimagnetic (FiM) order sets in below the Néel temperatureTFN∼ 77 K due to uneven moments of divalent Co (↑ 5.33µB) and tetravalent Mn (↓ 3.87µB) which coexists with transverse spin-glass state below 72.85 K. Such complicated magnetic behaviour is suggested to result from the competing anisotropic superexchange interactions (JAB/kB∼ 4.3 K,JAA/kB∼ -6.2 K andJBB/kB∼ -3.3 K) between the cations, which is extracted following the Néel's expression for the two-sublattice model of FiM. Dynamical susceptibility (χac(f, T)) and relaxation of thermoremanent magnetization,MTRM(t) data have been analysed by means of the empirical scaling-laws such as Vogel-Fulcher law and Power law of critical slowing down. Both of which reveal the reentrant spin-glass like character which evolves through a number of intermediate metastable states. The magnitude of Mydosh parameter (Ω âˆ¼ 0.002), critical exponentzυ= (6.7 ± 0.07), spin relaxation timeτ0= (2.33 ± 0.1) × 10-18s, activation energyEa/kB= (69.8 ± 0.95) K and interparticle interaction strength (T0= 71.6 K) provide the experimental evidences for canonical spin-glass state below the spin freezing temperatureTF= 72.85 K. The field dependence ofTFobtained fromχac(T) follows the irreversibility in terms of de Almeida-Thouless mean-field instability in which the magnitude of crossover scaling exponent Φ turns out to be ∼2.9 for the (Ge0.8Mn0.2)Co2O4. Isothermal magnetization plots reveal two field-induced transitions across 9.52 kOe (HSF1) and 45.6 kOe (HSF2) associated with the FiM domains and spin-flip transition, respectively. Analysis of the inverse paramagnetic susceptibilityχp-1χp=χ-χ0after subtracting the temperature independent diamagnetic termχ0(=-3 × 10-3emu mol-1Oe-1) results in the effective magnetic momentµeff= 7.654µB/f.u. This agrees well with the theoretically obtainedµeff= 7.58µB/f.u. resulting the cation distributionMn0.24+↓A[Co22+↑]BO4in support of the Hund's ground state spin configurationS=3/2andS= 1/2of Mn4+and Co2+, respectively. TheH-Tphase diagram has been established by analysing all the parameters (TF(H),TFN(H),HSF1(T) andHSF2(T)) extracted from various magnetization measurements. This diagram enables clear differentiation among the different phases of the (GeMn)Co2O4and also illustrates the demarcation between short-range and long-range ordered regions.

Probing the incoherent admixture of low and high-spin states of Co in (LaPr)CoO3perovskite: focus on structural phase transitions.

We report the mixed valence and intermediate spin-state (IS) transitions in Pr substituted LaCoO3perovskites in the form of bulk and nanostructures. Various compositions (x) of La1-xPrxCoO3(0 ⩽x⩽ 0.9) were synthesized using the sol-gel process under moderate heat treatment conditions (600 °C). The structural analysis of these compounds reveals a phase crossover from the monoclinic phase (space group, s.g.:I2/a) to an orthorhombic one (s.g.:Pbnm), and a rhombohedral phase (s.g.:R-3c) to an orthorhombic one (s.g.:Pnma) in the bulk and nanostructures, respectively, for the composition range 0 ⩽x⩽ 0.6. Such a structural transformation remarkably reduces the Jahn-Teller distortion factor ΔJT: 0.374 → 0.0016 signifying the dominant role of the IS state (SAvg= 1) of trivalent Co ions in the investigated system. Magnetization measurements reveal the ferromagnetic (FM) nature of bulk LaCoO3along with a weak antiferromagnetic (AFM) component coexisting with an FM component. This coexistence results in a weak loop-asymmetry (zero-field exchange-bias effect ∼134 Oe) at low temperatures. Here the FM ordering occurs due to the double-exchange interaction (JEX/kB∼ 11.25 K) between the tetravalent and trivalent Co ions. Significant decrease in the ordering temperatures was noticed in the nanostructures (TC∼ 50 K) as compared to the bulk counterpart (∼90 K) due to the finite size/surface effects in the pristine compound. However, the incorporation of Pr leads to the development of a strong AFM component (JEX/kB∼ 18.2 K) and enhances the ordering temperatures (∼145 K forx= 0.9) with negligible FM correlations in both bulk and nanostructures of LaPrCoO3due to the dominant super-exchange interaction: Co3+/4+‒O‒Co3+/4+. Further evidence of the incoherent mixture of low-spin (LS) and high-spin (HS) states comes from theM-Hmeasurements which yields a saturation magnetization ofMS∼ 275 emu mol-1(under the limit of 1/H→ 0) consistent with the theoretical value of 279 emu mol-1corresponding to the spin admixture: 65% LS + 10% IS of trivalent Co along with 25% of LS Co4+in the bulk pristine compound. A similar analysis yields: Co3+[30% LS + 20% IS] + Co4+[50% of LS] for the nanostructures of LaCoO3,yet the Pr substitution decreases the spin admixture configuration. The Kubelka-Munk analysis of the optical absorbance results in a significant decrease in the optical energy band gap (Eg:1.86 → 1.80 eV) with the incorporation of Pr in LaCoO3which corroborates the above results.