Enhanced conduction band density of states in intermetallic EuTSi3 (T = Rh, Ir).

We report on the physical properties of single crystalline EuRhSi3 and polycrystalline EuIrSi3, inferred from magnetization, electrical transport, heat capacity and (151)Eu Mössbauer spectroscopy. These previously known compounds crystallise in the tetragonal BaNiSn3-type structure. The single crystal magnetization in EuRhSi3 has a strongly anisotropic behaviour at 2 K with a spin-flop field of 13 T, and we present a model of these magnetic properties which allows the exchange constants to be determined. In both compounds, specific heat shows the presence of a cascade of two close transitions near 50 K, and the (151)Eu Mössbauer spectra demonstrate that the intermediate phase has an incommensurate amplitude modulated structure. We find anomalously large values, with respect to other members of the series, for the RKKY Néel temperature, for the spin-flop field (13 T), for the spin-wave gap (≃20-25 K) inferred from both resistivity and specific heat data, for the spin-disorder resistivity in EuIrSi3 (≃240 µΩ cm) and for the saturated hyperfine field (52 T). The enhanced values of the quantities that depend on the electronic density of states at the Fermi level, imply that the latter must be strongly enhanced in these two materials. EuIrSi3 exhibits a giant magnetoresistance ratio, with values exceeding 600% at 2 K in a field of 14 T.

Magnetic anisotropy, unusual hysteresis and putative "up-up-down" magnetic structure in EuTAl4Si2 (T = Rh and Ir).

We present detailed investigations on single crystals of quaternary EuRhAl4Si2 and EuIrAl4Si2. The two compounds order antiferromagnetically at TN1 = 11.7 and 14.7 K, respectively, each undergoing two magnetic transitions. The magnetic properties in the ordered state present a large anisotropy despite Eu(2+)being an S-state ion for which the single-ion anisotropy is expected to be weak. Two features in the magnetization measured along the c-axis are prominent. At 1.8 K, a ferromagnetic-like jump occurs at very low field to a value one third of the saturation magnetization (1/3 M0) followed by a wide plateau up to 2 T for Rh and 4 T for Ir-compound. At this field value, a sharp hysteretic spin-flop transition occurs to a fully saturated state (M0). Surprisingly, the magnetization does not return to origin when the field is reduced to zero in the return cycle, as expected in an antiferromagnet. Instead, a remnant magnetization 1/3 M0 is observed and the magnetic loop around the origin shows hysteresis. This suggests that the zero field magnetic structure has a ferromagnetic component, and we present a model with up to third neighbor exchange and dipolar interaction which reproduces the magnetization curves and hints to an "up-up-down" magnetic structure in zero field.

EuNiGe3, an anisotropic antiferromagnet.

Single crystals of EuNiGe3, crystallizing in the non-centrosymmetric BaNiSn3-type structure, were grown using In flux, enabling us to explore the anisotropic magnetic properties, which was not possible with previously reported polycrystalline samples. The EuNiGe3 single crystalline sample is found to order antiferromagnetically at 13.2 K, as revealed from the magnetic susceptibility, heat capacity and electrical resistivity data. The low temperature magnetization M (H) is distinctly different for the field parallel to the ab-plane and c-axis; the ab-plane magnetization varies almost linearly with the field before the occurrence of an induced ferromagnetic (FM) phase (spin-flip) at 6.2 Tesla. On the other hand M (H) along the c-axis is accompanied by two metamagnetic transitions followed by a spin-flip at 4.1 T. A model including anisotropic exchange and dipole-dipole interactions reproduces the main features of magnetization plots but falls short of full representation. (H,T) phase diagrams have been constructed for the field applied along the principal directions. From the (151)Eu Mössbauer spectra, we determine that the 13.2 K transition leads to an incommensurate antiferromagnetic (AFM) intermediate phase followed by a transition near 10.5 K to a commensurate AFM configuration.

Magnetization process in Er2Ti2O7 at very low temperature.

We present a model which accounts for the high-field magnetization at very low temperature in the frustrated pyrochlore compound Er2Ti2O7. In Er2Ti2O7, the Er(3+) ion has a planar crystal field anisotropy and the material undergoes a transition to antiferromagnetism at TN = 1.2 K. Our model is a mean-field self-consistent calculation involving the four rare earth sites of a tetrahedron, the building unit of the pyrochlore lattice. It includes the full crystal field Hamiltonian, the infinite range dipolar interaction and anisotropic nearest neighbour exchange described by a 4-component tensor. We discuss the equivalence of our treatment of the exchange tensor, taken to be diagonal in a frame linked to a rare earth-rare earth bond, with the pseudo-spin Hamiltonian recently developed for Kramers doublets in a pyrochlore lattice.

Dynamical splayed ferromagnetic ground state in the quantum spin ice Yb(2)Sn(2)O(7).

From magnetic, specific heat, (170)Yb Mössbauer effect, neutron diffraction, and muon spin relaxation measurements on polycrystalline Yb(2)Sn(2)O(7), we show that below the first order transition at 0.15 K all of the Yb(3+) ions are long-range magnetically ordered and each has a moment of 1.1 µ(B) which lies at ≃ 10° to a common fourfold cubic axis. The four sublattice moments have four different directions away from this axis and are therefore noncoplanar. We term this arrangement splayed ferromagnetism. This ground state has a dynamical component with a fluctuation rate in the megahertz range. The net ferromagnetic exchange interaction has an anisotropy that favors the local threefold axis. We discuss our results in terms of the phase diagram proposed by Savary and Balents [Phys. Rev. Lett. 108, 037202 (2012)] for a pyrochlore lattice of Kramers 1/2 effective spins.

Gapless spin liquid ground state in the S = 1/2 vanadium oxyfluoride kagome antiferromagnet [NH4]2[C7H14N][V7O6F18].

The vanadium oxyfluoride [NH(4)](2)[C(7)H(14)N][V(7)O(6)F(18)] (DQVOF) is a geometrically frustrated magnetic bilayer material. The structure consists of S = 1/2 kagome planes of V(4+) d(1) ions with S = 1 V(3+) d(2) ions located between the kagome layers. Muon spin relaxation measurements demonstrate the absence of spin freezing down to 40 mK despite an energy scale of 60 K for antiferromagnetic exchange interactions. From magnetization and heat capacity measurements we conclude that the S = 1 spins of the interplane V(3+) ions are weakly coupled to the kagome layers, such that DQVOF can be viewed as an experimental model for S = 1/2 kagome physics, and that it displays a gapless spin liquid ground state.

Singlet ground state of the quantum antiferromagnet Ba(3)CuSb(2)O(9).

We present local probe results on the honeycomb lattice antiferromagnet Ba(3)CuSb(2)O(9). Muon spin relaxation measurements in a zero field down to 20 mK show unequivocally that there is a total absence of spin freezing in the ground state. Sb NMR measurements allow us to track the intrinsic susceptibility of the lattice, which shows a maximum at around 55 K and drops to zero in the low-temperature limit. The spin-lattice relaxation rate shows two characteristic energy scales, including a field-dependent crossover to exponential low-temperature behavior, implying gapped magnetic excitations.

Antiferromagnetic ordering in EuPtGe3.

The magnetic properties of single crystalline EuPtGe(3), crystallizing in the non-centrosymmetric BaNiSn(3)-type crystal structure, have been studied by means of magnetization, electrical resistivity, heat capacity and (151)Eu Mössbauer spectroscopy. The susceptibility and heat capacity data indicate a magnetic transition at T(N) = 11 K. The Mössbauer data confirm this conclusion, but evidence a slight first-order character of the transition. Analysing the magnetization data using a mean field model with two antiferromagnetically coupled sublattices allows us to explain some aspects of the magnetic behaviour, and to derive the first- and second-neighbour exchange integrals in EuPtGe(3).

Ising versus XY anisotropy in frustrated R(2)Ti(2)O(7) compounds as "Seen" by Polarized Neutrons.

We studied the field induced magnetic order in R(2)Ti(2)O(7) pyrochlore compounds with either uniaxial (R=Ho, Tb) or planar (R=Er, Yb) anisotropy, by polarized neutron diffraction. The determination of the local susceptibility tensor {chi(parallel to),chi(perpendicular)} provides a universal description of the field induced structures in the paramagnetic phase (2-270 K), whatever the field value (1-7 T) and direction. Comparison of the thermal variations of chi(parallel to) and chi(perpendicular) with calculations using the rare earth crystal field shows that exchange and dipolar interactions must be taken into account. We determine the molecular field tensor in each case and show that it can be strongly anisotropic.

The Yb(2)Al(1-x)Mg(x)Si(2) series from a spin fluctuation (x = 0) to a magnetically ordered ground state (x = 1).

The structural and magnetic properties of Yb(2)Al(1-x)Mg(x)Si(2) (x = 0, 0.5 and 1), crystallizing in the tetragonal Mo(2)FeB(2)-type structure, are reported in this work. Yb(2)AlSi(2) exhibits a Pauli paramagnetic ground state arising due to spin/valence fluctuations induced by a significant Yb 4f conduction band hybridization. High-field magnetization (up to 120 kOe) indicates a nearly temperature-independent susceptibility of 8.6 × 10(-3) emu/Yb mol below 10 K. On the other hand, Yb ions in Yb(2)MgSi(2) order antiferromagnetically at a relatively high temperature T(N) of 9.5 K. The intermediate composition alloy Yb(2)Al(0.5)Mg(0.5)Si(2) is a Kondo lattice, antiferromagnet with T(N) = 5.5 K. The coefficient of the linear term of the electronic heat capacity, γ, of Yb(2)AlSi(2) is found to be 305 mJ mol(-1) K(-2), indicating a significant electronic mass enhancement due to strong electronic correlations. Below 12 K, an additional contribution to the heat capacity of the form T(3)lnT is observed. The (170)Yb Mössbauer spectra in the ordered state of Yb(2)MgSi(2) indicate a strong coupling of the 4f quadrupolar moment with the magnetic moment through a magneto-elastic coupling.

Anisotropic exchange in frustrated pyrochlore Yb(2)Ti(2)O(7).

The local Yb(3+) magnetic susceptibility tensor was recently measured in the frustrated pyrochlore compound Yb(2)Ti(2)O(7) by means of in-field polarized neutron scattering in a single crystal. A very anisotropic effective exchange tensor was derived for the Yb(3+) ion. Using this result, we reinterpret here the data for the powder susceptibility in Yb(2)Ti(2)O(7). We show that, in the case of a well-isolated Kramers doublet with anisotropic g and exchange tensors, the inverse susceptibility for a powder sample does not strictly obey a Curie-Weiss law at low temperature. We discuss the consequences regarding the paramagnetic Curie temperature, usually taken as a measure of the exchange/dipolar interaction, and the exotic 'slow fluctuation' ground state of Yb(2)Ti(2)O(7).

Field-induced spin-ice-like orders in spin liquid Tb2Ti2O7.

We have studied the field-induced magnetic structures in Tb2Ti2O7, in a wide temperature (0.3 < T < 270 K) and field (0 < H < 7 T) range, by single crystal polarized and unpolarized neutron diffraction, with H parallel[110] axis. A ferromagneticlike structure with k = 0 propagation vector is induced, whose local order at low field and low temperature is akin to spin ice. The four Tb ions separate in alpha and beta chains having different values of the magnetic moments, which is quantitatively explained by taking the crystal field anisotropy into account. Above 2 T and below 2 K, an antiferromagneticlike structure with k = (0,0,1) is induced besides the k = 0 structure. It shows a reentrant behavior and extends over a finite length scale. It occurs together with a broadening of the nuclear peaks, which suggests a field-induced distortion and magnetostriction effect.

Continuous production of water dispersible carbon-iron nanocomposites by laser pyrolysis: application as MRI contrasts.

Carbon encapsulated iron/iron-oxide nanoparticles were obtained using laser pyrolysis method. The powders were processed to produce stable and biocompatible colloidal aqueous dispersions. The synthesis method consisted in the laser decomposition of an aerosol of ferrocene solution in toluene. This process generated, in a continuous way and in a single step, a nanocomposite formed by amorphous carbon nanoparticles of 50-100 nm size in which isolated iron based nanoparticles of 3-10 nm size are located. The effect of using different carriers and additives was explored in order to improve the efficiency of the process. The samples after purification by solid-liquid extraction with toluene, were oxidised in concentrated nitric acid solution of sodium chlorate, washed and finally ultrasonically dispersed in 1 mM tri-sodium citrate solutions. The dispersions obtained have hydrodynamic particle size less than 150 nm and are stable in the pH range of 2-11. Finally the shortening of the transversal relaxation time of water protons produced by the dispersed particles was studied in order to test the feasibility of these systems to be traced by magnetic resonance imaging techniques.

Spectroscopic description of an unusual protonated ferryl species in the catalase from Proteus mirabilis and density functional theory calculations on related models. Consequences for the ferryl protonation state in catalase, peroxidase and chloroperoxidase.

The catalase from Proteus mirabilis peroxide-resistant bacteria is one of the most efficient heme-containing catalases. It forms a relatively stable compound II. We were able to prepare samples of compound II from P. mirabilis catalase enriched in (57)Fe and to study them by spectroscopic methods. Two different forms of compound II, namely, low-pH compound II (LpH II) and high-pH compound II (HpH II), have been characterized by Mössbauer, extended X-ray absorption fine structure (EXAFS) and UV-vis absorption spectroscopies. The proportions of the two forms are pH-dependent and the pH conversion between HpH II and LpH II is irreversible. Considering (1) the Mössbauer parameters evaluated for four related models by density functional theory methods, (2) the existence of two different Fe-O(ferryl) bond lengths (1.80 and 1.66 A) compatible with our EXAFS data and (3) the pH dependence of the alpha band to beta band intensity ratio in the absorption spectra, we attribute the LpH II compound to a protonated ferryl Fe(IV)-OH complex (Fe-O approximately 1.80 A), whereas the HpH II compound corresponds to the classic ferryl Fe(IV)=O complex (Fe=O approximately 1.66 A). The large quadrupole splitting value of LpH II (measured 2.29 mm s(-1) vs. computed 2.15 mm s(-1)) compared with that of HpH II (measured 1.47 mm s(-1) vs. computed 1.46 mm s(-1)) reflects the protonation of the ferryl group. The relevancy and involvement of such (Fe(IV)=O/Fe(IV)-OH) species in the reactivity of catalase, peroxidase and chloroperoxidase are discussed.

Microscopic study of a pressure-induced ferromagnetic-spin-glass transition in the geometrically frustrated pyrochlore (Tb1-xLax)2Mo2O7.

We have studied (Tb1-xLax)2Mo2O7 pyrochlores by neutron diffraction and muSR at ambient and under applied pressure. (Tb,La) substitution expands the lattice and induces a change from a spin-glass-like state (x=0) to a noncollinear ferromagnet (x=0.2). In the ferromagnetic structure, the Tb moments orient close to their local anisotropy axes as for an ordered spin ice, while the Mo ones orient close to the net moment. The temperature dependence of the muSR relaxation rates and static local fields suggests a second transition of dynamical nature below the Curie transition. Under pressure, the long range order breaks down and a spin-glass-like state is recovered. The whole set of data provides a microscopic picture of the spin correlations and fluctuations in the region of the ferromagnetic-spin-glass threshold.

Magnetic density of states at low energy in geometrically frustrated systems.

Using muon-spin-relaxation measurements we show that the pyrochlore compound Gd(2)Ti(2)O(7), in its magnetically ordered phase below approximately 1 K, displays persistent spin dynamics down to temperatures as low as 20 mK. The characteristics of the induced muon relaxation can be accounted for by a scattering process involving two magnetic excitations, with a density of states characterized by an upturn at low energy and a small gap depending linearly on the temperature. We propose that such a density of states is a generic feature of geometrically frustrated magnetic materials.

Planar spin fluctuations with a quadratic thermal dependence rate in spin liquid Gd3Ga5O12.

The spin liquid properties of Gd3Ga5O12 have been examined using 155Gd Mössbauer spectroscopy down to 0.027 K. Information has been obtained concerning both the directional properties of the short range correlated moments and the thermal dependence of their spin fluctuation rates. Each Gd3+ spin (S=7/2) is found to be confined to a plane and its fluctuation rate decreases from approximately 2.8 x 10(9) s(-1) at 0.4 K to approximately 0.03 x 10(9) s(-1) at 0.09 K following a close-to-quadratic thermal dependence.

First-order transition in the spin dynamics of geometrically frustrated Yb2Ti2O7.

Using neutron diffraction, 170Yb Mössbauer and muon spin relaxation spectroscopies, we have examined the pyrochlore Yb2Ti2O7, where the Yb3+S' = 1/2 ground state has planar anisotropy. Below approximately 0.24 K, the temperature of the known specific-heat lambda transition, there is no long range magnetic order. We show that the transition corresponds to a first-order change in the fluctuation rate of the Yb3+ spins. Above the transition temperature, the rate, in the GHz range, follows a thermal excitation law, whereas below, the rate, in the MHz range, is temperature independent, indicative of a quantum fluctuation regime.