Long-range magnetic order in Mn[N(CN)2]2(pyz) (pyz = pyrazine). Susceptibility, magnetization, specific heat, and neutron diffraction measurements and electronic structure calculations

Using dc magnetization, ac susceptibility, specific heat, and neutron diffraction, we have studied the magnetic properties of Mn[N(CN)2]2(pyz) (pyz = pyrazine) in detail. The material crystallizes in the monoclinic space group P2(1)/n with a = 7.3248(2), b = 16.7369(4), and c = 8.7905 (2) A, beta = 89.596 (2) degrees, V = 1077.65(7) A(3), and Z = 4, as determined by Rietveld refinement of neutron powder diffraction data at 1.35 K. The 5 K neutron powder diffraction data reflect very little variation in the crystal structure. Interpenetrating ReO3-like networks are formed from axially elongated Mn(2+) octahedra and edges made up of mu-bonded [N(CN)2](-) anions and neutral pyz ligands. A three-dimensional antiferromagnetic ordering occurs below T(N) = 2.53(2) K. The magnetic unit cell is double the nuclear one along the a- and c-axes, giving the (1/2, 0, 1/2) superstructure. The crystallographic and antiferromagnetic structures are commensurate and consist of collinear Mn(2+) moments, each with a magnitude of 4.15(6) mu(B) aligned parallel to the a-direction (Mn-pyz-Mn chains). Electronic structure calculations indicate that the exchange interaction is much stronger along the Mn-pyz-Mn chain axis than along the Mn-NCNCN-Mn axes by a factor of approximately 40, giving rise to a predominantly one-dimensional magnetic system. Thus, the variable-temperature magnetic susceptibility data are well described by a Heisenberg antiferromagnetic chain model, giving g = 2.01(1) and J/k(B) = -0.27(1) K. Owing to single-ion anisotropy of the Mn(2+) ion, field-induced phenomena ascribed to spin-flop and paramagnetic transitions are observed at 0.43 and 2.83 T, respectively.     

Spin ordering in the mixed-ligand antiferromagnet Mn(dca)2(pyrazine)

The flexibility offered by molecular-based systems allows us to introduce or replace specific ligands in a material with the aim of radically altering desired structural and magnetic properties. Specifically, Mn(dca)₂(pyz) {dca = dicyanamide, [N(CN)₂]⁻; PYZ = pyrazine} has a unique interpenetrating ReO₃-like lattice. The Mn²⁺ cations are high-spin ( ) and the material orders antiferromagnetically below T_N = 2.53(2) K. Using neutron powder diffraction we observed a collinear spin structure oriented along the short ac-diagonal of the monoclinic unit cell. Inelastic neutron scattering results show a magnetic excitation at 0.23 meV. The strong dispersion character of this excitation demonstrates that it is related to a low-energy spin wave. Upon warming, the magnon gradually softens and disappears at T_N, while critical scattering becomes evident by a broad quasielastic response above T_N. The energy of the magnon is consistent with the exchange parameter, J, derived from magnetic susceptibility measurements.     

Magnetic excitations in multiferroic TbMnO3: evidence for a hybridized soft mode

The magnetic excitations in multiferroic TbMnO3 have been studied by inelastic neutron scattering in the spiral and sinusoidally ordered phases. At the incommensurate magnetic zone center of the spiral phase, we find three low-lying magnons whose character has been fully determined using neutron-polarization analysis. The excitation at the lowest energy is the sliding mode of the spiral, and two modes at 1.1 and 2.5 meV correspond to rotations of the spiral rotation plane. These latter modes are expected to couple to the electric polarization. The 2.5 meV mode is in perfect agreement with recent infrared-spectroscopy data giving strong support to its interpretation as a hybridized phonon-magnon excitation.     

Quasiparticlelike peaks, kinks, and electron-phonon coupling at the (pi,0) regions in the CMR oxide La2-2x Sr1+2x Mn2 O7

Using angle-resolved photoemission, we have observed sharp quasiparticlelike peaks in the prototypical layered manganite La(2-2x)Sr(1+2x)Mn(2)O(7) (x=0.36,0.38). We focus on the (pi,0) regions of k space and study their electronic scattering rates and dispersion kinks, uncovering bilayer-split bands, the critical energy scales, momentum scales, and strengths of the interactions that renormalize the electrons. To identify these bosons, we measured phonon dispersions in the energy range of the kink by inelastic neutron scattering, finding a good match in both energy and momentum to the oxygen bond-stretching phonons.     

Revised superconducting phase diagram of hole-doped Na(x)(H3O)(z)CoO2 x yH(2)O

We have studied the superconducting phase diagram of NaxCoO2.yH(2)O as a function of electronic doping, characterizing our samples both in terms of Na content x and the Co valence state. Our findings are consistent with a recent report that intercalation of H3O+ ions into NaxCoO2, together with water, acts as an additional dopant, indicating that Na substoichiometry alone does not control the electronic doping of these materials. We find a superconducting phase diagram where optimal T(C) is achieved through a Co valence range of 3.24-3.35, while T(C) decreases for materials with a higher Co valence. The critical role of dimensionality in achieving superconductivity is highlighted by similarly doped nonsuperconducting anhydrous samples, differing from the superconducting hydrate only in interlayer spacing.     

Glass transition in the polaron dynamics of colossal magnetoresistive manganites

Neutron scattering measurements on a bilayer manganite near optimal doping show that the short-range polaron correlations are completely dynamic at high T, but then freeze upon cooling to a temperature T(*) approximately equal 310 K. This glass transition suggests that the paramagnetic/insulating state arises from an inherent orbital frustration that inhibits the formation of a long-range orbital- and charge-ordered state. Upon further cooling into the ferromagnetic-metallic state (T(C) = 114 K), where the polarons melt, the diffuse scattering quickly develops into a propagating, transverse optic phonon.     

A secretory phospholipase A2-mediated neuroprotection and anti-apoptosis

Background  

Phospholipase A₂ liberates free fatty acids and lysophospholipids upon hydrolysis of phospholipids and these products are often associated with detrimental effects such as inflammation and cerebral ischemia. The neuroprotective effect of neutral phospholipase from snake venom has been investigated.     

Raman and Neutron Scattering Study of Partially Deuterated L‐Alanine: Evidence of a Solid‐Solid Phase Transition

Raman and neutron experiments using specific isotope labeling were combined in order to study the dynamics and structure of L ‐alanine. Inelastic neutron and Raman scattering data of C₂H₄(ND₂)CO₂D are discussed in relation to the doubling of the lattice parameter a observed by means of neutron powder diffraction in C₂D₄ (NH₂)CO₂H. The major changes accompanying the phase transition are found in the vibrational frequencies involving the torsional vibration τ(CO₂^?), which is clearly affected by the hydrogen bonds between the protons of the ammonium group and the oxygen atoms of the carboxylate group. At lower temperatures the rearrangement of identifiable hydrogen bonds induces changes in the bending vibration δ(ND₃), confirming some orientational disorder.     

A low‐temperature neutron diffraction study of Mn12‐acetate

In the low‐temperature region, where the dodecanuclear mixed‐valence manganese carboxyl­ate hexa­deca­acetatotetra­aqua­dodeca­oxo­dodeca­manganese bis­(acetic acid) tetra­hydrate, [Mn₁₂O₁₂(C₂D₃O₂)₁₆(H₂O)₄]·2C₂HD₃O₂·4H₂O, displays unusual magnetic properties, its structure is similar to that previously determined at room temperature [Lis (1980). Acta Cryst. B 36 , 2042–2046], differing only by a small change in the configuration of one of the coordinated acetate groups, related to the formation of additional hydrogen bonds, and by the orientation of the methyl groups. Since most of the magnetization density of this system resides on the Mn atoms, the consequences of these rearrangements for the magnetic properties of the compound are small.     

Cycloidal order of 4f moments as a probe of chiral domains in DyMnO₃

Using soft x-ray diffraction at the Dy-M? resonance, pronounced circular dichroism in the ferroelectric phase of DyMnO? is observed in connection with sizable b and c components of the Dy-4f magnetic moments. This provides strong evidence for cycloidal order of the 4f moments, corroborating that inversion-symmetry breaking in this material is not accomplished by the Mn spins alone. The 4f circular dichroism allows us to image multiferroic domains that are imprinted on the surface of DyMnO? using the local charging by the x-ray beam via the photoelectric effect.