Electronic, magnetic, and vibrational properties of the molecular magnet Mn4 monomer and dimer

A new type of the single-molecule magnet [Mn₄O₃Cl₄(O₂CEt)₃(py)₃] forms dimers. Recent magnetic hysteresis measurements on this single-molecular magnet revealed interesting phenomena: an absence of quantum tunneling at zero magnetic field and tunneling before magnetic field reversal. This is attributed to a significant antiferromagnetic exchange interaction between different monomers. To investigate this system, we calculate the electronic structure, magnetic properties, intramolecular and intermolecular exchange interactions using density-functional theory within the generalized-gradient approximation. Our calculations agree with experiment. We find that the calculated threefold symmetric structure is vibrationally stable. We also calculate vibrational infrared absorption and Raman scattering intensities for the monomer which can be tested experimentally.     

Anisotropy dispersion in (CoCrPt)1−x(SiO2)x perpendicular recording media

The distribution of easy axis orientation in perpendicular media is of technological importance because it affects the value of S^* (see Fig. 1), which quantifies the switching field distribution (SFD) and hence partially determines the data density achievable on a given medium. The distribution is controlled by the crystallographic orientation of grains and factors such as intergranular exchange and dipolar coupling. Due to strong demagnetising fields in the perpendicular orientation, traditional measurements of remanence as a function of angle are difficult to interpret and have required the use of large-scale computational models. In this work we have utilised the variation of coercivity H_C with angle, which has the advantage that at H_C the global demagnetising field is zero. Additionally, since such materials follow essentially the Stoner–Wohlfarth mode of reversal, the variation of H_C with angle, H_C(θ), is much greater than that for the remanence. We find that for (CoCrPt)_1−x(SiO₂)_x, where the level of exchange coupling is controlled, the distribution of magnetic easy axes is narrower when the exchange coupling is reduced, but dipolar coupling between the grains is strong and affects the magnetisation reversal significantly.     

High-frequency permeability and permittivity of NixZn(1−x)Fe2O4 thick film

Magnetic materials such as Ni_xZn_(1−x)Fe₂O₄ have resonant frequency in high frequency; therefore, they are more useful especially in microwaves. The Ni_xZn_(1−x)Fe₂O₄ was prepared by the chemical coprecipitation method using citrate precursors, and the fritless thick film was screen printed on alumina substrates. The composition-dependent permeability and permittivity in the high frequency 8–12 GHz are investigated. Using the overlay technique on Ag-thick-film patch antenna, the change in reflectance and transmittance has been measured. The Ni_xZn_(1−x)Fe₂O₄ thick film, when used as overlay on Ag-thick-film patch antenna, changes the resonance characteristics. The changes in resonance frequency, reflectance and transmittance have been used to calculate the permeability and permittivity of the thick film. Zinc-concentration-dependent changes are obtained.     

Preparation of substituted barium ferrite BaFe12−x(Ti0.5Co0.5)xO19 by citrate precursor method and compositional dependence of their magnetic properties

As a possible candidate for the left-handed metamaterial with negative permeability, a series of Ti, Co-substituted M-type barium hexaferrite BaFe_12−x(Ti_0.5Co_0.5)_xO₁₉ (x=0, 1, 2, 3, 4 and 5) was prepared by citrate precursor method. The formation processes of the substituted barium hexaferrite compounds from the precursors were followed by the measurements of powder X-ray diffraction (XRD), Infrared absorption spectra (FT-IR), and thermogravimetry and differential thermal analysis (TG/DTA) coupled with mass spectroscopy (MS). In the case of the non-substituted sample, the formation of the barium hexaferrite is regulated by the thermal decomposition of BaCO₃ and the solid-state reactions of BaO and Fe₂O₃ in the temperature range from 800 to 1100 K. The formation temperature of the substituted BaFe_12−x(Ti_0.5Co_0.5)_xO₁₉ is higher than that for the non-substituted sample and increases with the value of x, due to the effects of carbonate ions incorporated by the partial substitution of Fe³⁺ by (Ti_0.5Co_0.5)³⁺. On heating up to ca. 1200 K, all the substituted samples transform into the magenetoplumbite phase as is the non-substituted sample. The compositional dependence of the magnetic properties of the substituted barium hexaferrite was investigated by the magnetization measurement. The decrease in the magnetic anisotropy was confirmed by the change in the magnetization curve and coercivity H_C with the composition x. A negative permeability spectrum was observed in the BaFe₉(Ti_0.5Co_0.5)₃O₁₉ in the frequency range from 2 to 4 GHz.     

Structural,microstructural and magnetic properties of nanocomposite isotropic Sm(CobalFe0.1MyZr0.04B0.04)7.5 ribbons with M=Ni,Cu and y=0.09 and 0.12

In boron-substituted melt-spun Sm(Co,Fe,Cu,Zr)_7.5-type alloys a nanocomposite microstructure and high coercivities in both as-spun and short-time annealed ribbons can be obtained. In the present study three different compositions, namely Sm(Co_0.73Fe_0.1Cu_0.09Zr_0.04B_0.04)_7.5, Sm(Co_0.70Fe_0.1Cu_0.12Zr_0.04B_0.04)_7.5 and Sm(Co_0.70Fe_0.1Ni_0.12Zr_0.04B_0.04)_7.5 have been examined in order to investigate the influence of composition on the magnetic properties and the microstructure. Melt-spun ribbons have been obtained and annealing has been followed under argon atmosphere for 30–75 min at 600–870 °C. For the as-spun ribbons the TbCu₇-type of structure and fcc-Co as a secondary phase have been identified in the X-ray diffraction patterns. For the annealed ribbons above 700 °C the 1:7 phase transforms into 2:17 and 1:5 phases. The TEM studies have shown a homogeneous nanocrystalline microstructure with average grain size of 30–80 nm. Coercivity values of 15–27 kOe have been obtained from hysteresis loops traced in non-saturating fields. The coercivity decreases with temperature, but it is sufficiently large to maintain values higher than 5 kOe at 380 °C.     

The use of symmetry in the search for canted ferromagnetism, its application to the molecular magnets Mn[N(CN)2]2 and Fe[N(CN)2]2

Canted ferromagnets present a important class of molecular magnets. In these materials the uncompensated magnetisation, created by the DzyaloshinskyMoriya interaction, has the particular property of being compatible with the symmetry of the underlying antiferromagnetic Hamiltonian. If the ordering transition is continuous, Landau theory and simple symmetry arguments about the crystal structure can be used to determine whether such parasitic ferromagnetism is possible, and therefore to aid the systematic search for new molecular ferromagnets.     

Structure and magnetic properties of (Nd,Dy)16(Fe,Co)76−xTixB8 powders prepared by mechanical alloying

Nanocrystalline (Nd,Dy)₁₆(Fe,Co)_76−xTi_xB₈ magnets were prepared by mechanical alloying and respective heat treatment at 973–1073 K/30–60 min. An addition of 0.5 at % of Ti results in an increase of coercivity from 796 to 1115 kA m⁻¹. Partial substitution of Nd by Dy results in an additional increase of coercivity up to 1234 kA m⁻¹. Mössbauer investigations shows that for x?1 the (Nd,Dy)₁₆(Fe,Co)_76−xTi_xB₈ powders are single phase. For higher Ti contents (x>1) the mechanically alloyed powders heat treated at 973 K are no more single phase, and the coercivity decreases due to the presence of an amorphous phase. A heat treatment at a higher temperature (1073 K) for longer time (1 h) results in the full recrystallisation of powders. The mean hyperfine field of the Nd₂Fe₁₄B phase decreases for titanium contents of 0?x?1, and remains constant for x>1. This indicates that the Ti content in the Nd₂Fe₁₄B phase reaches its maximum value.     

Effect of trivalent cation substitution for manganese upon ferromagnetism in Ln0.57Ca0.43MnO3 (Ln=Pr, Nd)

The substitution of small contents of trivalent cations for manganese in the oxides Ln_0.57Ca_0.43Mn_1−xM_xO₃ (Ln=Pr, Na) has been explored for M=Al, Ga, Fe, Cr, Sc, In. It is shown that similarly to Ba-doping, the M-doped Pr-manganites exhibit a great predisposition to ferromagnetism in a low magnetic field of 0.25 T, reaching ferromagnetic (FM) fractions of 85% for M=Ga and 100% for m=Cr, whereas in contrast only small FM fractions (∼8%) can be reached for the M-doped Nd-manganites. The great ability of both Pr and Nd manganites to exhibit ultrasharp steps at 2.5 K, at increasing magnetic field is also demonstrated. The different behaviors of the so-doped manganites are interpreted in terms of geometric effects (size of the A-sites cations and of the doping elements) and of electronic configurations and magnetic properties of the dopants.     

Ferromagnetic resonance studies on (Co40Fe40B20)x(SiO2)1−x granular magnetic films

Magnetic properties of granular (Co₄₀Fe₄₀B₂₀)_x(SiO₂)_1−x   thin films (x=0.37-0.53$x=0.37-0.53$) have been studied by ferromagnetic resonance (FMR) technique. Samples have been prepared by ion-beam deposition of Co–Fe–B particles and SiO₂ on sitall ceramic substrate. The FMR measurements have been done for different orientations of DC magnetic field with respect to the sample plane. It was found that the deduced value of effective magnetization from FMR data of the thin granular film is reduced by the volume-filling factor of the bulk saturation magnetization. The overall magnetization changes from 152 to 515 G depending on the ratio of the magnetic nanoparticles in the SiO₂ matrix. From angular measurements an induced in-plane uniaxial anisotropy has been obtained due to the preparation of the film conditions as well.     

Magnetotransport properties of (La0.7Pb0.3MnO3)1−xAgx composites

Magnetic and transport properties of (La_0.7Pb_0.3MnO₃)_1−xAg_x composites are explored in this study. Ferromagnetism is gradually attenuated due to the magnetic dilution with increase of Ag content percentage. Clearly irreversible behavior in the zero-field cooling and field cooling curves at a low field caused by the competition between the magnetization and magnetic domain orientation processes has been observed as x increases. Saturation magnetization decreases as x increases, while ferromagnetic transition temperature remains around 346 K for all composites. The resistivity decreases significantly for (La_0.7Pb_0.3MnO₃)_1−xAg_x composites. It is suggested that introduction of Ag into the niche of grain boundaries forms artificial conducting network and improves the carriers to transport. However, enhancement of magnetoresistance has been observed for the system.     

Structural and magnetic properties of Mg(In2−xMnx)O4 system

We synthesized the Mn-doped Mg(In_2−xMn_x)O₄ oxides with 0.03?x?0.55 using a solid-state reaction method. The X-ray diffraction patterns of the samples were in a good agreement with that of a distorted orthorhombic spinel phase. Their lattice parameters and unit-cell volumes decrease with x due to the substitution of the smaller Mn³⁺ ions to the larger In³⁺ ions. The undoped MgIn₂O₄ oxide presents diamagnetic signals for 5 K?T?300 K. The M(H) at T=300 K reveals a fairly negative-sloped linear relationship. Neither magnetic hysteresis nor saturation behavior was observed in this parent sample. For the Mn-doped samples, however, positive magnetization were observed between 5 and 300 K even if the x value is as low as 0.03. The mass susceptibility enhances with Mn content and it reaches the highest value of 1.4×10⁻³ emu/g Oe (at T=300 K) at x=0.45. Furthermore, the Mn-doped oxides with x=0.06 and 0.2, respectively, exhibit nonlinear magnetization curves and small hysteretic loops in low magnetic fields. Susceptibilities of the Mn-doped samples are much higher than those of MnO₂, Mn₂O₃ oxides, and Mn metals. These results show that the oxides have potential to be magnetic semiconductors.     

Transmission electron microscopy study of large field induced anisotropy (Co1−xFex)89Zr7B4 nanocomposite ribbons with dilute Fe-contents

Electron microscopy was employed to investigate the structure of magnetic field crystallized (Co_1−xFe_x)₈₉Zr₇B₄ alloys with only dilute Fe-contents (x=0, 0.025, 0.05, and 0.10). The x=0.025 and 0.05 alloys exhibit very large field induced anisotropies and multiple nanocrystalline phases (BCC, FCC, and HCP) surrounded by an intergranular amorphous phase. Correlation between the volume fraction crystallized and the measured value of H_K suggests that the large K_U values are associated with the crystalline phases that form. Multiple crystalline phases are present for the highest K_U alloys and so the presence of FCC and/or HCP-type nanocrystals may be responsible for these observations. High-resolution transmission electron microscopy (HRTEM) illustrates a number of microstructural features including (1) high densities of stacking faults in many of the FCC and, in particular, the HCP-type nanocrystals, (2) infrequent BCC/FCC orientation relationships, and (3) nanocrystals with disordered or long period stacking sequences of close-packed planes. High densities of planar faults are suggested as a potential source of K_U for the FCC and HCP-type nanocrystals, but the origin of the large values of K_U found in dilute Fe-containing, Co-rich “nanocomposite” alloys is an area where further work is needed.     

Magnetic susceptibility of (IPA)2FeCl4, (IBuA)2FeCl4 and (IPA)2CuCi4 (IPA = isopropylammonium ion and IBuA = isobutylammonium ion)

The magnetic susceptibility of (IPA)₂FeCl₄, (IBuA)₂FeCl₄ and (IPA)₂CuCl₄, where IPA = (CH₃)₂CHNH⁺₃ and IBuA = (CH₃)₂CHCH₂NH⁺₃, were measured in the temperature range form 80 K up to a temperature near the melting points of the samples. The results obtained were interpreted in termw of a canted two-dimensional antiferromagnet. The variation of the magnetic susceptibility with the change in the composition was also discussed.     

Permeability-frequency spectra of (Fe1−xcox)73.5Cu1Nb3Si13.5B9 nanocrystalline alloys under different magnetic fields

Under various amplitude of AC magnetic fields domain wall motion is the main mechanism in the magnetization process. This includes domain wall bulging and domain wall displacing. In this paper complex permeability-frequency spectra of (Fe_1−xCo_x)_73.5Cu₁Nb₃Si_13.5B₉ (x=0,0.5$x=0,0.5$) nanocrystalline alloys were measured as a function of the AC magnetic field, ranging from 0.001 to 0.04 Oe. Obvious changes have been found in complex permeability spectra for alloy x=0$x=0$ with the change of the amplitude of AC magnetic field, but variation of AC magnetic field has little effect on complex permeability spectra for alloy x=0.5$x=0.5$. This is attributed to the increased pinning field after substitution of Fe with Co in Fe_73.5Cu₁Nb₃Si_13.5B₉ nanaocrystalline alloy.     

Temperature dependence of magnetostriction in [Co1−x(FeNi)x]75Si15B10 amorphous alloys

Magnetostriction measurements as a function of temperature and composition are reported for [Co_1x(Fe_0.5Ni_0.5)_x]₇₅Si₁₅B₁₀ metallic glasses. Single-ion as well as two-ion contributions to λ_s are found in the composition range 0<x<0.5. For x=0.12 the magnetostriction changes sign with increasing temperature.     

Soft magnetic properties and giant magneto-impedance effect of Fe73.5−xCrxSi13.5B9Nb3Au1 (x=1–5) alloys

In this paper, the effect of microstructural and surface morphological developments on the soft magnetic properties and giant magneto-impedance (GMI) effect of Fe_73.5−xCr_xSi_13.5B₉Nb₃Au₁ (x=1, 2, 3, 4, 5) alloys was investigated. It was found that the Cr addition causes slight decrease in the mean grain size of α-Fe(Si) grains. AFM results indicated a large variation of surface morphology of density and size of protrusions along the ribbon plane due to structural changes caused by thermal treatments with increasing Cr content. Ultrasoft magnetic properties such as the increase of magnetic permeability and the decrease of coercivity were observed in the samples annealed at 540 °C for 30 min. Accordingly, the GMI effect was also observed in the annealed samples.     

Hydrogen bonds mediated magnetism in Cu(bmen)2Pd(CN)4

Results of synthesis, X-ray structure analysis, electron spin resonance, susceptibility, magnetization and specific heat measurements of powdered Cu(bmen)₂Pd(CN)₄ (,N^′-dimethyl-1,2-diaminoethane) are reported. Its structure is formed of quasi-linear chains of the [-Cu(bmen)₂-NC-Ni(CN)₂-CN-]_n composition; these are interlinked by hydrogen bonds (HBs) leading to two-dimensional patterns. Upon magnetic, spectral and thermodynamic measurements the compound was identified as an S=1/2 Heisenberg antiferromagnet on a square lattice with due to the dominant role of HBs in creating a square network. The long-range ordering observed at 0.24 K is proposed to be of a Néel type. The possibility of tuning the exchange interactions in various directions is considered.     

Luminescent properties of KGd1−x(WO4)2:Eux and KGd1−x(WO4)2−y(MoO4)y:Eux phosphors in UV-VUV regions

KGd_1−x(WO₄)_2−y(MoO₄)_y:Eu³⁺_x(0.1?x?0.75, y=0 and 0.2) phosphors are synthesized through traditional solid-state reaction and their luminescent properties in ultraviolet (UV) and vacuum ultraviolet (VUV) regions are investigated. Under 147 nm excitation, these phosphors show characteristic red emission with good color purity. In order to improve their emission intensity, the MoO₄²⁻ (20 wt%) is introduced into the anion of KGd_1−x(WO₄):Eu³⁺_x. The Mo⁶⁺ and Eu³⁺ co-doped KGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped KGd(WO₄)₂ in VUV region. The chromaticity coordination of KGd_0.45(WO₄):Eu³⁺_0.55 is (x=0.669, y=0.331), while that of KGd_0.45(WO₄)_1.8(MoO₄)_0.2:Eu³⁺_0.55 is (x=0.666, y=0.334) in VUV region.     

On the room-temperature ferromagnetism in (ZnO)0.98(MnO2)0.02

Room-temperature ferromagnetism (RTFM) is investigated in the polycrystalline bulk (ZnO)_0.98(MnO₂)_0.02 samples prepared by a modified solid-state sintering route. Successive sintering of a sample was carried out in air at different temperatures in the range of 400-1000 °C. The study of magnetization and phase-investigation in the sample was carried out after each sintering step. The progressive suppression of impurities and the consequent reduction in RTFM is clearly observed in the samples with increase in the sintering temperature up to 800 °C. The subsequent successive sintering of the (ZnO)_0.98(MnO₂)_0.02 sample up to 1000 °C yields fully paramagnetic sample exhibiting wurtzite structure. The studies support the conjecture (Kundaliya et al., Nat. Mater. 3 (2004) 709 [18]) that RTFM in this system has an origin related to a randomly distributed impurity phase produced by local dissolution of ZnO and MnO₂.