Phase diagram of the half-filled ionic Hubbard model

We study the phase diagram of the ionic Hubbard model (IHM) at half filling on a Bethe lattice of infinite connectivity using dynamical mean-field theory (DMFT), with two impurity solvers, namely, iterated perturbation theory (IPT) and continuous time quantum Monte Carlo (CTQMC). The physics of the IHM is governed by the competition between the staggered ionic potential Delta and the on-site Hubbard U. We find that for a finite Delta and at zero temperature, long-range antiferromagnetic (AFM) order sets in beyond a threshold U = U-AF via a first-order phase transition. For U smaller than U-AF the system is a correlated band insulator. Both methods show a clear evidence for a quantum transition to a half-metal (HM) phase just after the AFM order is turned on, followed by the formation of an AFM insulator on further increasing U. We show that the results obtained within both methods have good qualitative and quantitative consistency in the intermediate-to-strong-coupling regime at zero temperature as well as at finite temperature. On increasing the temperature, the AFM order is lost via a first-order phase transition at a transition temperature T-AF(U,Delta) or, equivalently, on decreasing U below U-AF(T,Delta)], within both methods, for weak to intermediate values of U/t. In the strongly correlated regime, where the effective low-energy Hamiltonian is the Heisenberg model, IPT is unable to capture the thermal (Neel) transition from the AFM phase to the paramagnetic phase, but the CTQMC does. At a finite temperature T, DMFT + CTQMC shows a second phase transition (not seen within DMFT + IPT) on increasing U beyond U-AF. At U-N > U-AF, when the Neel temperature T-N for the effective Heisenberg model becomes lower than T, the AFM order is lost via a second-order transition. For U >> Delta, T-N similar to t(2)/U(1 - x(2)), where x = 2 Delta/U and thus T-N increases with increase in Delta/U. In the three-dimensional parameter space of (U/t, T/t, and Delta/t), as T increases, the surface of first-order transition at U-AF(T,Delta) and that of the second-order transition at U-N(T,Delta) approach each other, shrinking the range over which the AFM order is stable. There is a line of tricritical points that separates the surfaces of first- and second-order phase transitions.

Structural-modulation-driven spin canting and reentrant glassy magnetic phase in ferromagnetic Lu2MnNiO6

Unusual behavior of reentrant spin-glass (RSG) compound Lu2MnNiO6 has been investigated by magnetometry and neutron diffraction. The system possesses a ferromagnetic (FM) ordering below 40 K and undergoes a RSG transition at 20 K. Additionally, Lu2MnNiO6 retains memory effect above the glassy transition till spins sustain ordering. A novel critical behavior with unusual critical exponents (beta =similar to 0.241 and gamma similar to 1.142) is observed that indicates a canting in the spin structure below the ferromagnetic transition (T-C). A comprehensive analysis of temperature-dependent neutron diffraction data and first-principles calculations divulge that a structural distortion induced by an octahedral tilting results in a canted spin structure below T-C.

Effect of Fe doping on the magnetic ordering temperature of ErMnO3

We studied the effect of Fe doping on structural, magnetic, and dielectric properties of hexagonal ErMnO3 system. For 50% doping of Fe on Mn site in ErMnO3 modulated its crystallographic structure from hexagonal to orthorhombic phase. Accompanied with the structural phase transition in ErMnO3, the magnetic properties are effectively modified. The Fe doped samples exhibit enhancement in antiferromagnetic ordering Neel temperature (T-N) from 77K (ErMnO3) to 280K (ErFe0.5Mn0.5O3). The anomalies observed in the dielectric constant around T-N in doped ErMnO3 samples indicate the coupling between electric and magnetic order parameters. (C) 2015 AIP Publishing LLC.

Temperature-Dependent Magnetic and EPR Studies of Bulk and Nanoparticles of Bi0.1Ca0.9MnO3

We report temperature-dependent magnetic and electron paramagnetic resonance (EPR) properties of bulk and nanoparticle samples of Bi0.1Ca0.9MnO3 (BCMO). The nanoparticles of BCMO (dia similar to 50 nm) were prepared by the standard sol-gel technique and bulk samples by solid-state reaction method. We have investigated the magnetic ordering in the two samples by carrying out temperature-dependent magnetic and EPR studies and compared their properties. According to earlier reports, antiferromagnetic and ferromagnetic orders coexist in the bulk sample of Bi0.1Ca0.9MnO3. Our magnetization and EPR results show the existence of ferromagnetism in the bulk sample which is present in the nanosample as well but with somewhat weakened strength with the size reduction.

Effect of Size Reduction on Magnetic Ordering in Sm1-x Ca (x) MnO3 (x=0.35, 0.65 and 0.92) Manganites: Magnetic and EMR Studies

We have employed the highly sensitive electron magnetic resonance technique complimented by magnetization measurements to study the impact of size reduction on the magnetic ordering in nanosized Sm1-x Ca (x) MnO3 (x = 0.35, 0.65 and 0.92). In the bulk form, x = 0.35 sample shows a charge ordering transition at 235 K followed by a mixed magnetic phase, the sample with x = 0.65 exhibits charge order below 275 K and shows an antiferromagnetic insulator phase below 135 K while that with x = 0.92 has a ferromagnetic-cluster glass ground state. Thus, a comparative study of magnetic ground states of bulk and nanoparticles (diameter similar to 25 nm) enables us to investigate size-induced effects on different types of magnetic ordering. It is seen that in the bulk samples the temperature dependences of the EPR parameters are quite different from each other. This difference diminishes for the nanosamples where all the three samples show qualitatively similar behavior. The magnetization measurements corroborate this conclusion.

Na2.44Mn1.79(SO4)(3): a new member of the alluaudite family of insertion compounds for sodium ion batteries

Sodium-ion batteries have been extensively pursued as economic alternatives to lithium-ion batteries. Investigating the polyanion chemistry, alluaudite structured Na2Fe2II(SO4)(3) has been recently discovered as a 3.8 V positive electrode material (Barpanda et al., Nature Commun., 5: 4358, 2014). Registering the highest ever Fe-III/Fe-II redox potential (vs. Na/Na+) and formidable energy density, it has opened up a new polyanion family for sodium batteries. Exploring the alluaudite family, here we report isotypical Na2+2xMn2-xII(SO4)(3) (x = 0.22) as a novel high-voltage cathode material for the first time. Following low-temperature (ca. 350 degrees C) solid-state synthesis, the structure of this new alluaudite compound has been solved adopting a monoclinic framework (s.g. C2/c) showing antiferromagnetic ordering at 3.4 K. Synergising experimental and ab initio DFT investigation, Na2+2xMn2-xII(SO4)(3) has been found to be a potential high-voltage (ca. 4.4 V) cathode material for sodium batteries.

New symmetrical dinucleating ligand based assembly of bridged dicopper(II) and dizinc(II) centers: Synthesis, structure, spectroscopy, magnetic properties and glycoside hydrolysis

Two dinuclear copper(II) complexes Li(H2O)(3)(CH3OH)](4)Cu2Br4]Cu-2(cpdp)(mu-O2CCH3)](4)(OH)(2) (1), Cu (H2O)(4)]Cu-2(cpdp)(mu-O2CC6H5)](2)Cl-2 center dot 5H(2)O (2), and a dinuclear zinc(II) complex Zn-2(cpdp)(mu-O2CCH3)] (3) have been synthesized using pyridine and benzoate functionality based new symmetrical dinucleating ligand, N, N'-Bis2-carboxybenzomethyl]-N, N'-Bis2-pyridylmethyl]-1,3-diaminopropan-2-ol (H(3)cpdp). Complexes 1, 2 and 3 have been synthesized by carrying out reaction of the ligand H3cpdp with stoichiometric amounts of Cu-2(O2CCH3)(4)(H2O)(2)], CuCl2 center dot 2H(2)O/C6H5COONa, and Zn(CH3COO)(2)center dot 2H(2)O, respectively, in methanol in the presence of NaOH at ambient temperature. Characterizations of the complexes have been done using various analytical techniques including single crystal X-ray structure determination. The X-ray crystal structure analyses reveal that the copper(II) ions in complexes 1 and 2 are in a distorted square pyramidal geometry with Cu-Cu separation of 3.455(8) angstrom and 3.492(1)angstrom, respectively. The DFT optimized structure of complex 3 indicates that two zinc(II) ions are in a distorted square pyramidal geometry with Zn-Zn separation of 3.492(8)angstrom. UV-Vis and mass spectrometric analyses of the complexes confirm their dimeric nature in solution. Furthermore, H-1 and C-13 NMR spectroscopic investigations authenticate the integrity of complex 3 in solution. Variable-temperature (2-300 K) magnetic susceptibility measurements show the presence of antiferromagnetic interactions between the copper centers, with J = -26.0 cm(-1) and -23.9 cm(-1) ((H) over cap = -2JS(1)S(2)) in complexes 1 and 2, respectively. In addition, glycosidase-like activity of the complexes has been investigated in aqueous solution at pH similar to 10.5 by UV-Vis spectrophotometric technique using p-nitrophenyl-alpha-D-glucopyranoside (4) and p-nitrophenyl-beta-D-glucopyranoside (5) as model substrates. (C) 2015 Elsevier B.V. All rights reserved.

Effect of Super-exchange Interaction on Ground state Magnetic Properties of Spin-dependent Falicov-Kimball Model on a Triangular Lattice

Ground state magnetic properties are studied by incorporating the super-exchange interaction (J(se)) in the spin-dependent Falicov-Kimball model (FKM) between localized (f-) electrons on a triangular lattice for half filled case. Numerical diagonalization and Monte-Carlo simulation are used to study the ground state magnetic properties. We have found that the magnetic moment of (d-) and (f-) electrons strongly depend on the value of Hund's exchange (J), super-exchange interaction (J(se)) and also depends on the number of (d-) electrons (N-d). The ground state changes from antiferromagnetic (AFM) to ferromagnetic (FM) state as we decrease (N-d). Also the density of d electrons at each site depends on the value of J and J(se).

Neutron diffraction, Mossbauer effect and Electron Paramagnetic Resonance studies on multiferroic Pb(Fe2/3W1/3)O-3

Multiferroic Pb(Fe2/3W1/3)O-3 ceramics were synthesized via a modified two-stage Columbite method. Single phase formation was confirmed from the analysis of x-ray and neutron diffraction patterns recorded at room temperature. Structural analysis of the diffraction data reveals cubic phase (space group Pm-3m) for the title compound. Magnetic structure of the title compound at room temperature exhibits G-type antiferromagnetic structure. The Mossbauer spectroscopy and Electron Paramagnetic Resonance (EPR) studies were carried out at 300 K. The isomer shift and quadrupole splitting of the Mossbauer spectra confirms the trivalent state of iron (Fe3+). The Mossbauer spectra also suggest that the iron and tungsten are randomly distributed at the octahedral, B site. EPR spectra show a single broad line associated with Fe3+ ions. Both spectra clearly exhibit weak ferromagnetic behaviour of Pb(Fe2/3W1/3)O-3 ceramic at 300 K. Considering neutron diffraction, Mossbauer and EPR results together, it may be stated here that Pb(Fe2/3W1/3)O-3 exhibits antiferromagnetic behavior along with weak ferromagnetism at room temperature.

Thermal, magnetic and electrical properties of Tb1-xDyxMnO3 multiferroics

A series of multiferroic materials with the compositional formula, Tb1 - xDyxMnO3 (where x=0, 0.1, 0.2, 0.3 and 0.4) were prepared by the sol gel method. After characterizing the samples structurally, a systematic investigation of specific heat, magnetization and dielectric properties over the temperature range, 4-300 K, was undertaken. Based on these studies, it was found that all the samples exhibit a transition at 40 K and the observed behavior may be attributed to the ordering of Mn3+ ions. Further, all the five samples are found to exhibit a ferroelectric transition in the temperature range 20-24 K. Finally, yet another transition was also exhibited by all the samples at temperatures below 10 K and is attributed to the antiferromagnetic (AF) ordering of rare-earth ionic moments. The magnetic entropy of all the samples was also computed with the help of their heat capacity data. (C) 2015 Elsevier B.V. All rights reserved.

The role of intra- and inter-site exchange correlations in the extended Falicov-Kimball model on a triangular lattice

Ground state magnetic properties of the spin-dependent Falicov-Kimball model (FKM) are studied by incorporating the intrasite exchange correlation J (between itinerant d- and localized f-electrons) and intersite (superexchange) correlation J (between localized f-electrons) on a triangular lattice for two different fillings. Numerical diagonalization and Monte-Carlo techniques are used to determine the ground state magnetic properties. Transitions from antiferromagnetic to ferromagnetic and again to re-entrant antiferromagnetic phase is observed in a wide range of parameter space. The magnetic moments of d- and f-electrons are observed to depend strongly on the value off, J and also on the total number of d-electrons (N-d). (C) 2015 Elsevier Ltd. All rights reserved.

Study of coexisting phases in Bi doped La0.67Sr0.33MnO3

We report the remarkable phase separation behavior in La0.67Sr0.33MnO3 doped with Bi3+ ion at La site. The temperature dependent resistivity and magnetization of La0.67-xBixSr0.33MnO3 (x>0) show the presence of phase separation of ferromagnetic metallic and charge ordered antiferromagnetic insulating phases. Markedly, the field dependant magnetization studies of La0.67-xBixSr0.33MnO3 (x=0.3) show the metamagnetic nature of ferromagnetic metallic state implying the competition of coexisting ferromagnetic metallic and charge ordered antiferromagnetic phases. The electron spin resonance and exchange bias studies of La0.67-xBixSr0.33MnO3 (x=0.4 and 0.5) substantiate the coexistence of ferromagnetic clusters in antiferromagnetic matrix. (C) 2016 Elsevier B.V. All rights reserved.

Magnetic structures and magnetic phase transitions in the Mn-doped orthoferrite TbFeO3 studied by neutron powder diffraction

The magnetic structures and the magnetic phase transitions in the Mn-doped orthoferrite TbFeO3 studied using neutron powder diffraction are reported. Magnetic phase transitions are identified at T-N(Fe/Mn) approximate to 295K where a paramagnetic-to-antiferromagnetic transition occurs in the Fe/Mn sublattice, T-SR(Fe/Mn) approximate to 26K where a spin-reorientation transition occurs in the Fe/Mn sublattice and T-N(R) approximate to 2K where Tb-ordering starts to manifest. At 295 K, the magnetic structure of the Fe/Mn sublattice in TbFe0.5Mn0.5O3 belongs to the irreducible representation Gamma(4) (G(x)A(y)F(z) or Pb'n'm). A mixed-domain structure of (Gamma(1) + Gamma(4)) is found at 250K which remains stable down to the spin re-orientation transition at T-SR(Fe/Mn) approximate to 26K. Below 26K and above 250 K, the majority phase (>80%) is that of Gamma(4). Below 10K the high-temperature phase Gamma(4) remains stable till 2K. At 2 K, Tb develops a magnetic moment value of 0.6(2) mu(B)/f.u. and orders long-range in F-z compatible with the Gamma(4) representation. Our study confirms the magnetic phase transitions reported already in a single crystal of TbFe0.5Mn0.5O3 and, in addition, reveals the presence of mixed magnetic domains. The ratio of these magnetic domains as a function of temperature is estimated from Rietveld refinement of neutron diffraction data. Indications of short-range magnetic correlations are present in the low-Q region of the neutron diffraction patterns at T < T-SR(Fe/Mn). These results should motivate further experimental work devoted to measure electric polarization and magnetocapacitance of TbFe0.5Mn0.5O3. (C) 2016 AIP Publishing LLC.

Anomalous re-entrant glassy magnetic phase in LaMn0.5Co0.5O3 single crystals

We report an anomalous re-entrant glassy magnetic phase in (l00) oriented ferromagnetic LaMn0.5Co0.5O3 single crystals. The characterization is fortified with conventional magnetometry, like linear as-well-as non-linear ac susceptibility and specific heat. As the sample is cooled below the ferromagnetic transition temperature, it reenters a glassy magnetic phase whose dynamics have little resemblance with the conventional response. The glassy transition shifts to a higher temperature with increasing frequency of the applied ac field. But it does not respond to the dc biasing or memory experiment. Specific heat as well as non-linear ac susceptibility data also do not relate to the conventional glassy response. Unusually low magnetic entropy indicates the lack of long range magnetic ordering. The results demonstrate that the glassy phase in LaMn0.5Co0.5O3 is not due to any of the known conventional origins. We infer that the competing ferromagnetic and antiferromagnetic interaction due to high B-site disorder is responsible for this anomalous re-entrant glassy phase. (C) 2016 AIP Publishing LLC.

Magnetic structures and magnetic phase transitions in the Mn-doped orthoferrite TbFeO3 studied by neutron powder diffraction

The magnetic structures and the magnetic phase transitions in the Mn-doped orthoferrite TbFeO3 studied using neutron powder diffraction are reported. Magnetic phase transitions are identified at T-N(Fe/Mn) approximate to 295K where a paramagnetic-to-antiferromagnetic transition occurs in the Fe/Mn sublattice, T-SR(Fe/Mn) approximate to 26K where a spin-reorientation transition occurs in the Fe/Mn sublattice and T-N(R) approximate to 2K where Tb-ordering starts to manifest. At 295 K, the magnetic structure of the Fe/Mn sublattice in TbFe0.5Mn0.5O3 belongs to the irreducible representation Gamma(4) (G(x)A(y)F(z) or Pb'n'm). A mixed-domain structure of (Gamma(1) + Gamma(4)) is found at 250K which remains stable down to the spin re-orientation transition at T-SR(Fe/Mn) approximate to 26K. Below 26K and above 250 K, the majority phase (>80%) is that of Gamma(4). Below 10K the high-temperature phase Gamma(4) remains stable till 2K. At 2 K, Tb develops a magnetic moment value of 0.6(2) mu(B)/f.u. and orders long-range in F-z compatible with the Gamma(4) representation. Our study confirms the magnetic phase transitions reported already in a single crystal of TbFe0.5Mn0.5O3 and, in addition, reveals the presence of mixed magnetic domains. The ratio of these magnetic domains as a function of temperature is estimated from Rietveld refinement of neutron diffraction data. Indications of short-range magnetic correlations are present in the low-Q region of the neutron diffraction patterns at T < T-SR(Fe/Mn). These results should motivate further experimental work devoted to measure electric polarization and magnetocapacitance of TbFe0.5Mn0.5O3. (C) 2016 AIP Publishing LLC.