Anisotropic magnetic exchange in orthorhombic RCu2 compounds (R = rare earth)

The magnetic excitations in the field induced ferromagnetic phase F3 of a NdCu₂ single crystal were investigated by means of inelastic neutron scattering experiments. A mean field model using the random phase approximation in connection with anisotropic magnetic bilinear R-R (R denotes a rare earth) exchange interactions is proposed to account for the observed dispersion. The relevance of this model to the analysis of the magnetic ordering process in other RCu₂ compounds is discussed. Received 21 April 1999     

Crystal-chemistry aspects and electric-field-gradient (EFG) dispersion in Ca-gallogermanate-type structures studied by Mössbauer spectroscopy

The crystal field disorder in some trigonal germanates of the type X_3-yLn_yFe_2+yGe_4-yO₁₄ (X = Ba, Sr; Ln = La, Nd; y = 0, 1) is studied by ⁵⁷Fe M?ssbauer effect. The dispersion of the electric field gradient (EFG) at the octahedral sites of these compounds is investigated. A correlation of the experimental and calculated EFG data with some crystal-chemistry aspects is presented. Received 3 February 1999     

Bromine metallization studied by X-ray absorption spectroscopy

The experimental data carried out by M?ssbauer and magnetic resonances investigations of the structural phase transitions in K₂ZnCl₄ crystals are discussed by a simple electrostatic model, calculating, the lattice contributions to the local electric potential V(r), electric field intensity E(r) and electric field gradient tensor, (r) and taking into account both the fractional electric point charges and rigid lattice approximations. The validity of the model is proved by a good fit of the computing results and experimental data of quadrupole splitting parameters at K sites obtained by ³⁹K-NMR methods in high temperature incommensurate phase ( Pnam symmetry). The experimental results obtained by M?ssbauer and EPR methods in commensurate phase (Pna2₁ symmetry) of iron and copper doped K₂ZnCl₄ crystals are explained by relaxing the rigid lattice approximation. The insertion of probe ions appear to be done on not-exactly-Zn²⁺ site. Received 3 February 1999 and Received in final form 4 May 1999     

Magnetic properties of Yb Mo O and Gd Mo O from rare earth Mössbauer measurements

Using ¹⁷⁰Yb and ¹⁵⁵Gd M?ssbauer measurements down to ∼ 0.03 K, we have examined the semiconducting pyrochlore Yb₂Mo₂O₇ where the Mo intra-sublattice interaction is anti-ferromagnetic and the metallic pyrochlore Gd₂Mo₂O₇ where this interaction is ferromagnetic. Additional information was obtained from susceptibility, magnetisation and ¹⁷²Yb perturbed angular correlation measurements. The microscopic measurements evidence lattice disorder which is important in Yb₂Mo₂O₇ and modest in Gd₂Mo₂O₇. Magnetic irreversibilities occur at 17 K in Yb₂Mo₂O₇ and at 75 K in Gd₂Mo₂O₇ and below these temperatures the rare earths carry magnetic moments which are induced through couplings with the Mo sublattice. In Gd₂Mo₂O₇, we observe the steady state Gd hyperfine populations at 0.027 K are out of thermal equilibrium, indicating that Gd and Mo spin fluctuations persist at very low temperatures. Frustration is thus operative in this essentially isotropic pyrochlore where the dominant Mo intra-sublattice interaction is ferromagnetic. Received 13 January 2003 Published online 4 June 2003 RID="a" ID="a"e-mail: hodges@drecam.saclay.cea.fr     

The spin-crossover complex [Fe(tpa)(NCS) 2 ]

The temperature-induced spin crossover of iron(II) in the [ Fe ( tpa )( NCS ) ₂ ] complex has been investigated by nuclear forward scattering (NFS), nuclear inelastic scattering (NIS), extended X-ray absorption fine structure (EXAFS) spectroscopy, conventional M?ssbauer spectroscopy (MS) and by measurements of the magnetic susceptibility (SQUID). The various measurements consistently show that the transition is complete and abrupt and exhibits a hysteresis between 102 and 110 K. The dependence of the hyperfine parameters of the high-spin (HS) and of the low-spin (LS) phase on temperature is gradual while the effective thickness (determined by the Lamb-M?ssbauer factor f _LM ) shows a step at the transition temperature. This step could be identified clearly because the effective thickness is measured directly by NFS. The Lamb-M?ssbauer factor, the Debye temperature and the mean-square displacement of iron(II) could be determined for the HS and for the LS phase. When comparing the NIS data with the results from density functional theory (DFT), the Fe-N stretching vibrations of both LS and HS phases could be unambiguously identified and the f _LM could be factorized for both phases into a lattice and a molecular part. The structural information from EXAFS and DFT geometry optimization are in reasonable agreement. Received 19 June 2001     

Hyperfine interactions at 181Hf(→181Ta) impurities implanted in Er2O3 and Gd2O3: structural and electronic dependence of the EFG in bixbyite sesquioxides

The time-differential-perturbed γ-γ angular-correlation technique (TDPAC) with ion-implanted ¹⁸¹Hf tracers has been applied to study the hyperfine interactions of ¹⁸¹Ta impurities in the cubic bixbyite structure of Er ₂ O ₃ and Gd ₂ O ₃ . The TDPAC experiments were performed in air in the temperature range 300-1073 K (in the case of Er ₂ O ₃ ) and 300-1173 K (in the case of Gd ₂ O ₃ ). Three electrical-quadrupole interactions were found in each oxide in the whole studied temperature range. Two of them were attributed to the electric-field gradients (EFG) acting on ¹⁸¹Ta probes substitutionally located on the two nonequivalent free-of-defects cation sites of the bixbyite structure. The EFG results are compared with predictions of the point-charge model and discussed together with previous results obtained with the probes ¹¹¹Cd and ¹⁸¹Ta in other isomorphous sesquioxides. The temperature dependence of the hyperfine parameters for both oxides is also discussed in terms of dilatometric expansion data. Received 29 December 2000 and Received in final form 8 March 2001     

Magnetic phase transition and magnetic structure of ground state in CsDyW O

Magnetic phase transition in the CsDyW₂O₈ magnet has been studied by means of low temperature specific heat C ( T ) measurements. The magnetic ordering temperature of the Dy³⁺ sublattice was established to be 1.34 K. The experimental results indicate on the antiferromagnetic character of interactions between Dy³⁺ ions. The behavior of the C ( T ) dependencies above and below T _N is discussed in frames of different theoretical models. The measurements data on temperature and field dependencies of magnetization are used to calculate the exchange and dipole-dipole interactions energy and to determine the possible magnetic structure of the ground state. Received 7 January 2002 / Received in final form 15 May 2002 Published online 7 September 2002     

Radioactive ions for solid-state investigations at magnetic surfaces and interfaces

Hyperfine interactions observed at isomeric states of radioactive probe nuclei are used as a tool for solid-state investigations. This method is sensitive to atomic-scale properties. In recent years surface and interface investigations using radioactive probes delivered many results which can hardly be achieved by any other method. Several groups, e.g., from Konstanz, Leuven, Groningen, Aarhus, Uppsala, Tel Aviv, Pennsylvania, contributed to this field. Our group studies magnetic properties at surfaces and interfaces performing perturbed angular correlation (PAC) measurements in the UHV chamber ASPIC (Apparatus for Surface Physics and Interfaces at CERN). We take advantage of the enhanced variety of PAC probes delivered by the on-line mass separator ISOLDE. First, we report on measurements of magnetic hyperfine fields ( B _hf) at Se adatoms on a ferromagnetic substrate using ⁷⁷Se as a PAC probe. The investigation of induced magnetic interactions in nonmagnetic materials is a further subject of our studies. Here the nonmagnetic 4d element Pd is investigated, when it is in contact with ferromagnetic nickel. An outlook will be given on studies to be done in the future. The experiments were performed at the HMI, Berlin, and at CERN, Geneva. Received: 1 May 2001 / Accepted: 4 December 2001     

Low temperature Kondo reduction of quadrupolar and magnetic moments in the YbCuAl series

We present measurements in the YbCu_5-xAl_x series, down to the 50 mK range, using ¹⁷⁰Yb M?ssbauer absorption spectroscopy and magnetisation measurements. In this series, the hybridisation between the Yb 4 f electrons and the conduction electrons is known to decrease as the Al content x increases. We apply the variational solution of the impurity Kondo problem to the interpretation of our data. We show that the Kondo temperature can be derived from the measured 4 f quadrupole moment and, for the magnetically ordered compounds (), we obtain the exchange energy as a function of the Al content. Our findings are in general agreement with Doniach's model describing the onset of magnetic ordering according to the relative values of the Kondo and exchange energy scales. Received 16 April 1998     

Non-Langevin behaviour of the uncompensated magnetization in nanoparticles of artificial ferritin

The magnetic behaviour of nanoparticles of antiferromagnetic artificial ferritin has been investigated by ⁵⁷Fe M?ssbauer absorption spectroscopy and magnetization measurements, in the temperature range 2.5-250 K and with magnetic fields up to 7 T. Samples containing nanoparticles with an average number of ⁵⁷Fe atoms ranging from 400 to 2 500 were studied. By analysing the magnetic susceptibility and zero field M?ssbauer data, the anisotropy energy per unit volume is found, in agreement with some of the earlier studies, to have a value typical for ferric oxides, i.e. a few 10⁵ ergs/cm³. By comparing the results of the two experimental methods at higher fields, we show that, contrary to what is currently assumed, the uncompensated magnetization of the ferritin cores in the superparamagnetic regime does not follow a Langevin law. For magnetic fields below the spin-flop field, we propose an approximate law for the field and temperature variation of the uncompensated magnetization, which was early evoked by Néel but has so far never been applied to real antiferromagnetic systems. More generally, this approach should apply to randomly oriented antiferromagnetic nanoparticles systems with weak uncompensated moments. Received 20 January 2000     

Antiferromagnetic resonance and high magnetic field properties of NaNiO2

Magnetisation measurements up to 23 T and submillimeter wave ESR in the frequency region 48-380 GHz have been performed on NaNiO₂ powders at low temperature. Also typical spectra above the Néel temperature are shown. At 4 K the magnetisation shows a spin-flop transition at 1.8 T and saturation at 10 T. /Ni confirms the low spin state of the Ni³⁺ ions. The susceptibility exhibits a maximum at K with and K. NaNiO₂ is an A-type antiferromagnet: we derive K and K for the interactions between Ni ions within and between adjacent layers, respectively. The AFMR spectra yield an energy gap of 52.5 GHz, in agreement with the spin-flop value derived from the magnetisation. The anisotropy of the g factor observed at 100 K with can be attributed to the Jahn-Teller effect for Ni³⁺ ions in the low spin state, which stabilises the occupation. We finally comment on the isomorphic controversial Li_1-xNi_1+xO₂ compound. Received 9 March 2000 and Received in final form 13 July 2000.     

Time-domain interferometry using synchrotron radiation applied to diffusion in ordered alloys

Time-domain interferometry of synchrotron radiation (TDI) has recently been used as a tool for investigating diffusion in glasses. This work deals with an extension of this technique to ordered structures. In a TDI experiment performed on the B2 alloy CoGa at the APS the intensity scattered into Bragg directions showed no detectable quasielastic signal. Experimental lower limits of the elastic contribution are given. They are in accordance with the coherent scattering function derived in this paper. This result indicates that TDI can be applied to diffusion in crystalline solids, e.g. intermetallic alloys, by using diffuse scattering. Requirements and limitations of diffuse scattering experiments are discussed. Received 21 September 2000 and Received in final form 13 December 2000     

Magnetic order in LaEuSrCuO studied [2pt] by Fe Mössbauer spectroscopy

⁵⁷Fe M?ssbauer effect studies of La_1.65Eu_0.20Sr_0.15CuO₄ doped with 0.5 at% ⁵⁷Fe performed in the temperature region 300 K > T > 4.2 K give an onset temperature for magnetic ordering of K. This temperature practically is the same as that found in Nd doped La_2-xSr_xCuO₄. It indicates that the magnetic ordering temperature in the LTT phase of rare earth (RE) doped La_2-xSr_xCuO₄ is independent of the RE moment. The direction of the ⁵⁷Fe magnetic moment in the magnetically ordered state is within the CuO₂ plane, while it has been found to be parallel to the c-axis in Nd doped La_2-xSr_xCuO₄. Received: 23 June 1998 / Accepted: 14 July 1998     

Ab initio determination of an extended Heisenberg Hamiltonian in CuO 2 layers

Accurate ab initio calculations on embedded Cu₄O₁₂ square clusters, fragments of the La₂CuO₄ lattice, confirm a value of the nearest neighbor antiferromagnetic coupling (J = 124 meV) previously obtained from ab initio calculations on bicentric clusters and in good agreement with experiment. These calculations predict non negligible antiferromagnetic second-neighbor interaction (J' = 6.5 meV) and four-spin cyclic exchange (K = 14 meV), which may affect the thermodynamic and spectroscopic properties of these materials. The dependence of the magnetic coupling on local lattice distortions has also been investigated. Among them the best candidate to induce a spin-phonon effect seems to be the movement of the Cu atoms, changing the Cu-Cu distance, for which the variation of the nearest neighbor magnetic coupling with the Cu-O distance is Δ J /Δ d _{Cu - O} ∼ 1700 cm^-1?^-1. Received 20 November 2000     

Electron paramagnetic resonance and magnetic susceptibility of rare-earth hydrazone compounds

The magnetic properties of the rare earth molecular compounds with hydrazone ligands containing Nd³⁺, Gd³⁺, and Yb³⁺ have been investigated by electron paramagnetic resonance (EPR) and magnetization measurements. For the Gd-compound, partially resolved fine structure due to Gd³⁺ and exchange narrowing effects at low temperatures are observed in the EPR spectra, suggesting, consistent with the EPR and dc magnetic susceptibility, weak antiferromagnetic exchange interactions. Paramagnetic behavior sustained down to low temperatures is derived for Yb³⁺ ions, whereas substantial ferromagnetic exchange coupling is inferred for the lighter Nd³⁺ ions, indicating significant variations of the exchange integrals along the lanthanide series. Received 29 April 2002 Published online 31 July 2002     

Magnetic properties and 119Sn hyperfine interaction parameters of LiMn6Sn6

We have synthesized LiMn₆Sn₆, the first RMn₆Sn₆ compound involving an alkali metal as R element. It crystallizes in the hexagonal (P6/mmm) HfFe₆Ge₆-type structure. From magnetic measurements and powder neutron diffraction experiments it is found that LiMn₆Sn₆ magnetically orders at T_C = 380 K in a simple easy-plane ferromagnetic structure (m_Mn = 2.58 μ_B at 2 K). The ¹¹⁹Sn M?ssbauer spectrum recorded at 5 K indicates that the tin nuclei experience huge hyperfine fields (as large as 35 T). Electronic structure calculations are used to gain information about the microscopic origin of both the hyperfine field and electric field gradient at the Sn nuclei. The former arises due to spin-dependent hybridization between the 5s states of Sn and the 3d states of Mn. The latter comes from the 5p charge density close to the nucleus, whose anisotropy is mainly produced through directional interactions with the 3d states of the first Mn neighbors. Comparison between experimental quadrupole splittings and theoretical electric field gradients allows us to propose a value of for the quadrupole moment of the first excited state (I= 3/2) of the ¹¹⁹Sn nucleus.     

Continuous canonical transformation for the double exchange model

The method of continuous canonical transformation is applied to the double exchange model with a purpose to eliminate the interaction term responsible for non conservation of magnon number. Set of differential equations for the effective Hamiltonian parameters is derived. Within the lowest order (approximate) solution we reproduce results of the standard (single step) canonical transformation. Results of the selfconsistent numerical treatment are compared with the other known studies for this model.     

Magnetic interaction in Mg, Ti, Nb doped manganites

An effect of Mn substitution with Me=Mg²⁺, Ti⁴⁺, Nb⁵⁺ in manganites has been investigated by preparing La_0.7Sr_0.3(Mn_1-xMe_x)O₃ and La_1-xSr_x(Mn_{1 - x/2}Nb_x/2)O₃ series. It was established that substitution of manganese with magnesium up to x = 0.16 leads to a collapse of a long-range ferromagnetic order whereas La_0.7Sr_0.3(Mn ^{3 +} _0.85Nb ^{5 +} _0.15)O₃ is ferromagnet with T _C = 123 K and exhibits a large magnetoresistance below Curie point despite an absence of four-valent manganese. Hypothetical magnetic phase diagrams are constructed for La_0.7Sr_0.3(Mn_1-xMe_x)O₃ and La_1-xSr_x(Mn_{1 - x/2}Nb_x/2)O₃. Our results show that Mn³⁺-O-Mn³⁺ exchange interaction is ferromagnetic in the orbitally disordered manganites as well as an increase of Mn⁴⁺ content above 50% from a total amount of manganese ions leads to formation of a spin glass state due to a competition between antiferromagnetic Mn⁴⁺-O-Mn⁴⁺ and ferromagnetic Mn³⁺-O-Mn⁴⁺(Mn³⁺) superexchange interactions. Received 24 January 2002 Published online 9 July 2002