A temperature and magnetic field dependence Mössbauer study of ɛ-Fe2O3

ɛ-Fe2O3 was synthesized as nanoparticles by a pre-vacuum heat treatment of yttrium iron garnet (Y3Fe5O12) in a silica matrix at 300-C followed by sintering in air at 1,000-C for up to 10 h. It displays complex magnetic properties that are characterized by two transitions, one at 480 K from a paramagnet (P) to canted antiferromagnet (CAF1) and the second at ca. 120 K from the canted antiferromagnet (CAF1) to another canted antiferromagnet (CAF2). CAF2 has a smaller resultant magnetic moment (i.e. smaller canting angle) than CAF1. Analysis of the zero-field Mossbauer spectra at different temperatures shows an associated discontinuity of the hyperfine field around 120 K. In an applied field, the different magnetic sublattices were identified and the directions of their moments were assigned. The moments of the two sublattices are antiparallel and collinear at 160 K but are at right angle to each other at 4.2 K

CuI–Br Oligomers and Polymers Involving Cu–S(cystamine) Bonds

The syntheses, crystal structures, and thermal properties of five cuprous bromides derived from cystamine, [NH3(CH2)2SS(CH2)2NH3]2+, here denoted by (SS), are reported. Whereas (SS)2Cu4Br8 (1) is a polar tetramer and (SS)2Cu2Br6 (2) consists of [(SS)Cu2Br6]2– dimers, α1-(SS)Cu2Br4 (3), (SS)Cu3Br5 (4), and α2-(SS)Cu2Br4 (5) are polymers; 3 and 5 are one-dimensional and 4 has a corrugated 2D network. All the compounds contain corner-shared tetrahedra with Cu–Br–Cu connections, and in some cases, edge-shared with double bromine bridges. The copper coordination is tetrahedral, either CuBr4 or CuBr3S, except in one case, in which trigonal geometry was encountered. Compounds 1, 2, and 4, which are synthesized at 50 °C, display Cu–S bonds with the cystamine through either one or both sulfur atoms. On the other hand, 3 and 5, which are synthesized at 80 °C, do not have any. There is a high tendency to form hydrogen bonds between the polar ammonium heads of the cystamine with the bromine atoms. The range of phases experienced in this system is related to the bifunctional nature of cystamine, which is characterized by its primary ammonium ends and its disulfide bridge, and to the subtle competition between Br– and S–S ligands towards the CuI ions, which appears to be controllable by temperature. The presence of both chiral M- and P-helicoidal conformers of cystamine in 1–5 results in racemic compounds adopting centrosymmetric structures for 1, 3, 4, and 5 but 2 adopts a noncentrosymmetric structure (P212121) resulting from the coordination of copper ions to one conformer; the other conformer is noncoordinated and acts as the counterion

Mössbauer and magnetic study of Co x Fe3−x O4 nanoparticles

Magnetic nanoparticles of cobalt ferrites Co x Fe3−x O4 (x = 1 or 2) have been obtained either by mechanical milling or thermal treatment of pre-prepared layered double hydroxide carbonate x-LDH–CO3. Mechanical milling of the 1-LDH–CO3 leads to the large-scale preparation of nearly spherical nanoparticles of CoFe2O4, the size of which (5 to 20 nm) is controlled by the treatment time. Core-shell structure with surface spin-canting has been considered for the nanoparticles formed to explain the observed hysteresis loop shift (from ZFC–FC) in the magnetic properties. Annealing treatment of the 2-LDH–CO3 below 673 K results in the formation of nearly spherical pure Co2FeO4 nanoparticles. At 673 K and above, the LDH decomposition leads to the formation of a mixture of both spinels phases Co2FeO4 and CoFe2O4, the amount of the latter increases with annealing temperature. Unusually high magnetic hardness characterized by a 22 kOe coercive field at 1.8 K has been observed, which reflects the high intrinsic anisotropy for Co2FeO4

Quantum and Thermal Phase Transitions of Halogen-Bridged Binuclear Transition-Metal Complexes

Aiming to settle the controversial observations for halogen-bridged binuclear transition-metal (MMX) complexes, finite-temperature Hartree-Fock calculations are performed for a relevant two-band Peierls-Hubbard model. Thermal, as well as quantum, phase transitions are investigated with particular emphasis on the competition between electron itinerancy, electron-phonon interaction and electron-electron correlation. Recently observed distinct thermal behaviors of two typical MMX compounds Pt_2(CH_3CS_2)_4I and (NH_4)_4[Pt_2(P_2O_5H_2)_4I]2H_2O are supported and further tuning of their electronic states is predicted.Comment: 5 pages, 3 figures embedded, to be published in J. Phys. Soc. Jpn. Vol.70, No.5 (2001

An Experimental and Semi-Empirical Method to Determine the Pauli-Limiting Field in Quasi 2D Superconductors as applied to κ\kappa-(BEDT-TTF)2_2Cu(NCS)2_2: Strong Evidence of a FFLO State

We present upper critical field data for $\kappa$-(BEDT-TTF)$_2$Cu(NCS)$_2$ with the magnetic field close to parallel and parallel to the conducting layers. We show that we can eliminate the effect of vortex dynamics in these layered materials if the layers are oriented within 0.3 degrees of parallel to the applied magnetic field. Eliminating vortex effects leaves one remaining feature in the data that corresponds to the Pauli paramagnetic limit ($H_p$). We propose a semi-empirical method to calculate the $H_p$ in quasi 2D superconductors. This method takes into account the energy gap of each of the quasi 2D superconductors, which is calculated from specific heat data, and the influence of many body effects. The calculated Pauli paramagnetic limits are then compared to critical field data for the title compound and other organic conductors. Many of the examined quasi 2D superconductors, including the above organic superconductors and CeCoIn$_5$, exhibit upper critical fields that exceed their calculated $H_p$ suggesting unconventional superconductivity. We show that the high field low temperature state in $\kappa$-(BEDT-TTF)$_2$Cu(NCS)$_2$ is consistent with the Fulde Ferrell Larkin Ovchinnikov state.Comment: 8 pages, 9 figures, 10 years of dat

Competing Ground States of the New Class of Halogen-Bridged Metal Complexes

Based on a symmetry argument, we study the ground-state properties of halogen-bridged binuclear metal chain complexes. We systematically derive commensurate density-wave solutions from a relevant two-band Peierls-Hubbard model and numerically draw the the ground-state phase diagram as a function of electron-electron correlations, electron-phonon interactions, and doping concentration within the Hartree-Fock approximation. The competition between two types of charge-density-wave states, which has recently been reported experimentally, is indeed demonstrated.Comment: 4 pages, 5 figures embedded, to appear in J. Phys. Soc. Jp

13C NMR study of superconductivity near charge instability realized in beta"-(BEDT-TTF)4[(H3O)Ga(C2O4)3]C6H5NO2

To investigate the superconducting (SC) state near a charge instability, we performed ^{13}C NMR experiments on the molecular superconductor beta"-(BEDT-TTF)_{4}[(H_{3}O)Ga(C_{2}O_{4})_{3}]C_{6}H_{5}NO_{2}, which exhibits a charge anomaly at 100 K. The Knight shift which we measured in the SC state down to 1.5 K demonstrates that Cooper pairs are in spin-singlet state. Measurements of the nuclear spin-lattice relaxation time reveal strong electron-electron correlations in the normal state. The resistivity increase observed below 10 K indicates that the enhanced fluctuation has an electric origin. We discuss the possibility of charge-fluctuation-induced superconductivity.Comment: 5 pages, 4 figure

Characterization of halogen-bridged binuclear metal complexes as hybridized two-band materials

We study the electronic structure of halogen-bridged binuclear metal (MMX) complexes with a two-band Peierls-Hubbard model. Based on a symmetry argument, various density-wave states are derived and characterized. The ground-state phase diagram is drawn within the Hartree-Fock approximation, while the thermal behavior is investigated using a quantum Monte Carlo method. All the calculations conclude that a typical MMX compound Pt_2(CH_3CS_2)_4I should indeed be regarded as a d-p-hybridized two-band material, where the oxidation of the halogen ions must be observed even in the ground state, whereas another MMX family (NH_4)_4[Pt_2(P_2O_5H_2)_4X] may be treated as single-band materials.Comment: 16 pages, 11 figures embedded, to be published in Phys. Rev.

Structure and magnetic properties of the AB(HCO2)3 (A = Rb+ or Cs+, B = Mn2+, Co2+ or Ni2+) frameworks: probing the effect of size on the phase evolution of the ternary formates

This work reports the synthesis and structures of six new AB(HCO2)3 (A = Rb+ or Cs+ and B = Mn2+, Co2+ or Ni2+) frameworks containing the largest monoatomic cations on the A-site. RbMn(HCO2)3 is found to adopt a distorted perovskite framework with a 412[middle dot]63 topology and a mixture of syn-anti and anti-anti ligands, while the remaining compounds adopt a chiral hexagonal structure with a 49[middle dot]66 topology. The structures of these frameworks clarify the effect of ionic size on the formation of the five known architectures adopted by the AB(HCO2)3 frameworks, which have attracted attention as a new class of potential multiferroics, and in particular the chiral hexagonal structure within this. This also highlights the role of molecular A-site cations in stabilising the 49[middle dot]66 topology for frameworks where such cations are too large or small to support this structure on the basis of size alone, possibly due to hydrogen bonding. The magnetic properties of the RbB(HCO2)3 and CsMn(HCO2)3 frameworks are also reported with the Rb+ compounds featuring weak ferromagnetic behaviour and the latter being purely antiferromagnetic. In conjunction with a comparison of the other isostructural AB(HCO2)3 frameworks we find that compounds adopting the 49[middle dot]66 topology have much higher magnetic ordering temperatures than those with the RbMn(HCO2)3 structure, highlighting the importance of understanding the structure-property relationships of the ternary formates

Soliton excitations in halogen-bridged mixed-valence binuclear metal complexes

Motivated by recent stimulative observations in halogen (X)-bridged binuclear transition-metal (M) complexes, which are referred to as MMX chains, we study solitons in a one-dimensional three-quarter-filled charge-density-wave system with both intrasite and intersite electron-lattice couplings. Two distinct ground states of MMX chains are reproduced and the soliton excitations on them are compared. In the weak-coupling region, all the solitons are degenerate to each other and are uniquely scaled by the band gap, whereas in the strong-coupling region, they behave differently deviating from the scenario in the continuum limit. The soliton masses are calculated and compared with those for conventional mononuclear MX chains.Comment: 9 pages, 10 figures embedded, to be published in J. Phys. Soc. Jpn. 71, No. 1 (2002