Ac Susceptibility Measurements Research Articles

Single-Molecule Magnet Behavior and Spin Structure of an FeIII7 Cartwheel Cluster Revealed by Sub-Kelvin Magnetometry and Mössbauer Spectroscopy: The Final Pieces of the Puzzle.

The spin frustration and other magnetic properties of the "cartwheel" heptanuclear cluster [FeIII7O3(O2CtBu)9(Me-dea)3(H2O)3] (Me-deaH2 = N-methyldiethanolamine) have been previously investigated; we present here a Mössbauer spectroscopic study and sub-Kelvin magnetization and ac susceptibility measurements which enable a complete magnetic picture of this frustrated cluster. 57Fe Mössbauer spectra above 150 K showed three doublets in a 1:3:3 ratio, which could be assigned by their respective quadrupole splittings to the central Fe(1) and the peripheral Fe(2) and Fe(3). The field dependence of the corresponding magnetic sextets at 3 K showed that the spins on the central Fe(1) and the three peripheral Fe(2) sites with O5N coordination are oriented mutually coparallel, while these are antiparallel to the spins on the peripheral Fe(3) sites with O6 coordination, resulting in an overall S = 5/2 ground state. This provides experimental confirmation of the previously proposed spin ground state structure. Upon cooling to sub-Kelvin temperatures, a crossover to spin blocking with TB ≈ 0.21 K could be observed. This single-molecule magnet behavior had been expected but had not been observable with a conventional SQUID. The anisotropy barrier, of 3-fold symmetry, can be described in terms of the parameter D/kB = -0.47 K and a fourth-order perturbation; the latter enables thermally activated quantum tunneling through the excited sublevel mz = ± 3/2, with an activation barrier of U/kB = 1.9 K.

Unveiling the impact of Ni doping on the structural, electronic, and magnetic properties of nanocrystalline FeCo2O4spinel oxide: A combined experimental andab initioinvestigations.

In the present work, nanocrystalline samples of compositions 〖Ni〗_x 〖Fe〗_(1-x) 〖Co〗_2 O_4 (x = 0.0, 0.25, 0.50, and 0.75) have been synthesized via co-precipitation method by annealing at 900 oC. The nanocrystalline samples of compositions Ni0.25Fe0.75Co2O4 (D0.25) and Ni0.5Fe0.5Co2O4 (D0.5) crystallize in a pure spinel phase, whereas Ni0.75Fe0.25Co2O4 (D0.75) show the existence of secondary phase of NiO, as confirmed by the X-ray diffraction analysis. The particle size and lattice strain in the samples both decrease as Ni substitution is increased. The field-dependent dc magnetization M(H) virgin curve measured at 5 K for sample D0.75 shows the existence of field-induced metamagnetic transition, while this behavior is absent in samples D0.5 and D0.25. Dynamic magnetic properties have been investigated by ac susceptibility measurement, which shows a strong frequency dependence behavior resulting from the blocking/spin-glass freezing states depending upon the amount of Ni substitution and the range of measurement temperature. High-resolution X-ray photoelectron spectroscopy (HR-XPS) analysis reveals the presence of mixed valence states of Fe2+/Fe3+, Co2+/Co+3, and Ni2+/Ni+3 in all samples. Using first principles-based Density Functional Theory (DFT) calculations with HSE06 exchange-correlation functional predicts the correct description of ground state which is ferrimagnetic and insulating in their inverse spinel case for D0.25, D0.5, and D0.75 samples that agreed well with our experimental observations. A closer look at the electronic structure near the Fermi level (EF) of Ni-doped samples suggests a typical Mott-Hubbard insulating state while it is found to be a mixture of charge-transfer and Mott-Hubbard insulating state for parent compound FeCo2O4. The obtained spin-dependent gap hierarchy can have possible application in spintronics. We have studied a detailed correlation between experiment and theory.

Slow Magnetic Relaxation in a Californium Complex.

We report the synthesis and characterization of the macrocyclic californium derivative Na[Cf(H2O)(DOTA)] (DOTA = 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate), 1-Cf, which was studied in comparison to its dysprosium counterpart, Na[Dy(H2O)(DOTA)], 1-Dy. Divergent spectroscopic and magnetic behaviors were observed between 1-Cf and 1-Dy. Based upon spectroscopic measurements, we propose that accessible 5f → 6d transitions (potentially operating in tandem with charge-transfer transitions) are the major contributors to the observed broadband photoluminescence in 1-Cf. Dc magnetic susceptibility data for 1-Cf revealed lower magnetic moments than those previously observed for 1-Dy and expected for an f9 free ion, which calculations suggest is the result of greater ligand field effects. Notably, 1-Cf displays slow magnetic relaxation on the time scale of ac susceptibility measurements, making it the first example of a californium-based single-molecule magnet. A side-by-side comparison of the ac susceptibility data reveals magnetic relaxation properties that widely differ between 1-Cf and 1-Dy. This divergent relaxation behavior is attributed mainly to the inherent difference in spin-orbit coupling between Dy3+ and Cf3+.

Planar XY magnetic glass state in the Gd2ScNbO7 pyrochlore

Here a spin glass system with emergent planar ordered spin clusters is investigated. The mixed B-site pyrochlore Gd2ScNbO7has been synthesized and characterized through a variety of techniques, including x-ray diffraction, magnetic susceptibility, muon spin relaxation, heat capacity and neutron scattering. Despite a Curie-Weiss temperature of -3.93(3) K, indicating net antiferromagnetic interactions, no signs of long ranged magnetic ordering are found down toT= 0.3 K. Instead, a disordered magnetic state emerges with a small correlation length of 2.1(1) Å of single tetrahedra. A Reverse Monte Carlo analysis of the polarized neutron scattering data reveals short-range antiferromagnetic order with emergent XY spin ordering similar to the parent pyrochlore compounds. Muon spin relaxation, and AC susceptibility measurements confirm that the magnetization condenses into a glass, with 10 % of the potential entropy missing in the specific heat. This magnetic ground state is similar to what is observed in Gd2Sn2O7just above the ordering temperature, without the eventual long-range ordering at low temperature.

Freezing of short-range ordered antiferromagnetic clusters in the CrFeTi2O7system.

We report on the CrFeTi2O7(CFTO) system using a combination of x-ray diffraction, dc magnetization, ac susceptibility, specific heat and neutron diffraction measurements. CFTO is seen to crystallize in a monoclinic P21/a symmetry. It shows a glassy freezing at Tf ~ 22 K, characterized by the observation of bifurcation between ZFC and FC χ (T) curves, frequency dispersion across Tf in ac susceptibility, and follows Vogel-Fulcher and power law type critical dynamics, very slow relaxation of iso-thermal remanent magnetization with time and the absence of an anomaly in the temperature dependence of specific heat measurements. The microscopic neutron diffraction analysis of CFTO not only confirms the absence of long-range antiferromagnetic ordering but also exhibits diffuse scattering due to the presence of short-range ordered antiferromagnetically correlated spin clusters.&#xD.

Evidence for vertical line nodes in Sr2RuO4 from nonlocal electrodynamics

By determining the superconducting lower and upper critical fields Hc1(T) and Hc2(T), respectively, in a high-purity spherical Sr2RuO4 sample via ac-susceptibility measurements, we obtain the temperature dependence of the coherence length ξ and the penetration depth λ down to 0.04Tc. Given the high sample quality, the observed T2 dependence of λ at low temperatures cannot be explained in terms of impurity effects. Instead, we argue that the weak type-II superconductor Sr2RuO4 has to be treated in the nonlocal limit. By comparing our data with existing theory in that limit, the penetration depth in Sr2RuO4 agrees with a gap structure having vertical line nodes, while horizontal line nodes cannot account for the observation. The work highlights the potential benefits of purifying other unconventional superconductors in order to access the fascinating nonlocal regime in more materials and to determine their Cooper pair wave functions. Published by the American Physical Society 2024

Triple-Decker Hexaazamacrocyclic Lanthanide(III) Complexes: Structure, Magnetic Properties, and Temperature-Dependent Luminescence.

The reaction of fluoride anions with mononuclear rare-earth(III) complexes of the hexaazamacrocycle derived from 2,6-diformylpyridine and ethylenediamine affords trinuclear coordination compounds [Ln3L3(μ2-F)4(NO3)2](NO3)3. The X-ray crystal structures of these complexes show triplex cationic complexes where the three roughly parallel macrocyclic lanthanide(III) units are linked by bis-μ2-F bridges. The detailed analysis of the photophysical properties of the [Eu3L3(μ2-F)4(NO3)2](NO3)3·2H2O and [Tb3L3(μ2-F)4(NO3)2](NO3)3·3H2O complexes reveals different temperature dependence of luminescence intensity and luminescence decay time of the Eu(III) and Tb(III) derivatives. The spectra of mixed species of average composition [Eu1.5Tb1.5L3(μ2-F)4(NO3)2](NO3)3·3H2O are in accordance with the ratiometric luminescent thermometer behavior. Measurements of the direct-current (dc) magnetic susceptibility of the [Dy3L3(μ2-F)4(NO3)2](NO3)3·2H2O complex indicate possible ferromagnetic interactions between the Dy(III) ions. Alternating current (ac) susceptibility measurements of this complex indicate single-molecule magnet behavior in zero dc field with magnetic relaxation dominated by Orbach mechanism and an effective energy barrier Ueff = 12.3 cm-1 (17.7 K) with a pre-exponential relaxation time, τ0 of 7.3 × 10-6 s. A similar reaction of mononuclear macrocyclic complexes with a higher number of fluoride equivalents results in polymeric {[Ln3L3(μ2-F)5](NO3)4}n complexes. The X-ray crystal structure of the Nd(III) derivative of this type shows trinuclear units that are additionally linked by single fluoride bridges to form a linear coordination polymer.

Investigations of magnetic and thermal expansion properties of two cobalt(II) metal-organic frameworks constructed by mixed bipyridyl-tetracarboxylate strategy

We report the syntheses, crystal structures, adsorption behavior, thermal expansion behavior, and magnetic properties of two cobalt(II) metal-organic frameworks (MOFs), {[Co(btca)1/2(bpe)(H2O)2]·bpe}n (1) and {Co(btca)1/2(bpe)(DMF)}n (2, H4btca = 1,2,4,5-benzenetetracarboxylic acid; bpe = 1,2-di(4-pyridyl)ethane), constructed using mixed bipyridyl and tetracarboxylate ligands. Single-crystal X-ray diffraction (SC-XRD) indicates that the change of synthetic solvents leads to a significant tuning of structural dimensionality from 2D to 3D framework. Temperature-dependent SC-XRD reveals anisotropically negative and positive thermal expansion of the compounds identified along different crystallographic axes within the frameworks over a 120–400 K temperature range. N2 adsorption measurements indicate a nonporous and ultramicroporous framework for 1 and 2, respectively. Magnetic measurements indicate an easy-plane magnetic anisotropy of the Co2+ ions in the MOFs, with experimental D values of 63.1 and 87.1 cm−1. The ac susceptibility measurements of 1 and 2 show field-induced slow magnetic relaxation below 6 K through different relaxation dynamics. This work not only provides two new cobalt(II) SIM-MOFs, but also presents an effective bipyridyl-tetracarboxylate strategy for designing and building framework materials with interesting magnetic and mechanical properties.

Non-Debye Behavior of the Néel and Brown Relaxation in Interacting Magnetic Nanoparticle Ensembles.

We used ac-susceptibility measurements to study the superspin relaxation in Fe3O4/Isopar M nanomagnetic fluids of different concentrations. Temperature-resolved data collected at different frequencies, χ″ vs. T|f, reveal magnetic events both below and above the freezing point of the carrier fluid (TF = 197 K): χ″ shows peaks at temperatures Tp1 and Tp2 around 75 K and 225 K, respectively. Below TF, the Néel mechanism is entirely responsible for the superspin relaxation (as the carrier fluid is frozen), and we found that the temperature dependence of the relaxation time, τN(Tp1), is well described by the Dorman-Bessais-Fiorani (DBF) model: τNT=τrexp⁡EB+EadkB T. Above TF, both the internal (Néel) and the Brownian superspin relaxation mechanisms are active. Yet, we found evidence that the effective relaxation times, τeff, corresponding to the Tp2 peaks observed in the denser samples do not follow the typical Debye behavior described by the Rosensweig formula 1τeff=1τN+1τB. First, τeff is 5 × 10-5 s at 225 K, almost three orders of magnitude more that its Néel counterpart, τN~8 × 10-8 s, estimated by extrapolating the above-mentioned DBF analysis. Thus, 1τN≫1τeff, which is clearly not consistent with the Rosensweig formula. Second, the observed temperature dependence of the effective relaxation time, τeff(Tp2), is excellently described by τB-1T=Tγ0exp⁡-E'kBT-T0', a model solely based on the hydrodynamic Brown relaxation, τB(T)=3ηTVHkBT, combined with an activation law for the temperature variation of the viscosity, ηT=η0exp⁡E'/kB(T-T0'. The best fit yields γ0=3ηVHkB = 1.6 × 10-5 s·K, E'/kB = 312 K, and T0' = 178 K. Finally, the higher temperature Tp2 peaks vanish in the more diluted samples (δ ≤ 0.02). This indicates that the formation of larger hydrodynamic particles via aggregation, which is responsible for the observed Brownian relaxation in dense samples, is inhibited by dilution. Our findings, corroborating previous results from Monte Carlo calculations, are important because they might lead to new strategies to synthesize functional magnetic ferrofluids for biomedical applications.

Unusual superconductivity in crystallographically disordered RT2−xSn2 compounds

The discovery of new superconducting materials represents a complementary and crucial tile to shed light on the mechanism controlling the phenomenon of superconductivity. During the search for new superconducting materials, we discovered a new series of intermetallic compounds with the general composition RZn2−xSn2 (R = La, Ce, Pr, Nd). Their formation and crystal structure have been investigated. The Zn content decreases along the series from ≈ 1.50 in LaZn1.50(1)Sn1.98(2) to ≈ 1.32 in NdZn1.321(8)Sn2.01(2), due to the partial occupation of one of the two Zn sites [the Zn1 (2c) site, which from ≈ 50% in the La compound drops to ≈ 42%, ≈ 37% and ≈ 32% in the Ce, Pr and Nd compounds, respectively]. Both the Zn occupation factor and unit cell volume follow the lanthanide contraction. No such compound has been observed with Sm. AC and DC magnetic susceptibility and transport measurements revealed LaZn1.5Sn2 to undergo a sharp superconducting transition at Tc = 5.5 K. In order to search for further possible superconductive homologues, the lanthanum substituted phases La(Zn,T)2–xSn2 (T = Ti, Mn, Fe, Co, Ni, Cu, Pd, Ag, Pt, Au, Cd; x ≈ 0.5) were also prepared. The crystal structure of the ternary compounds is a disordered defective derivative of the tetragonal CaBe2Ge2-type (tP10, P4/nmm), with a partially occupied Zn Wyckoff site and a disordered Sn position. Three related isostructural series, corresponding to three new prototypes, have been identified; they all contain conventional checkered pyramidal layers characteristic of the archetype. The magnetic and transport properties have been measured for some of these substituted quaternary La compounds and we found that superconductivity is preserved in them but in the orthorhombic compounds or when T was a magnetic transition metal (e.g., Ni or Mn). A slight decrease in Tc down to about 4.0 K was detected as a result of the Zn by T atomic substitution.

Pinning Energy and Evidence of Granularity in the AC Susceptibility of an YBa2Cu3O7-x Superconducting Film

The study of granularity in superconducting films by using AC susceptibility has a crucial role in the development of and improvement in the ReBCO-coated conductors, which are a constantly evolving reality in the modern power applications of superconductivity. Specifically, the study of the granularity is essential because the ReBCO superconducting wires and tapes are far from the regularity of a single crystal while they often present an inter- and intragranular contribution to the critical current density. On the other hand, the AC susceptibility is a key part of the characterization of a granular sample because this technique is very sensitive to the presence of granularity in the superconductors and, moreover, the study of its first harmonic allows for determining pivotal properties such as the pinning energy as well as the dissipation processes acting in the sample. The pinning energy values and the granularity of an YBCO thin film have been studied by means of AC susceptibility measurements as a function of the AC amplitude, temperature, and DC field. In particular, the first harmonic imaginary component of the AC susceptibility χ1″ related to the dissipation processes of the sample has been studied. First, starting from the Brandt approach, the critical current density Jc and the pinning energy U of the sample have been extracted at 77 K by using the χ1″ measurements as a function of the AC amplitude at different AC frequencies and DC fields. From these measurements, a first signal of granularity appears. In order to confirm it, the temperature dependence of the χ1″ at different DC fields has been studied and a contribution deriving from the inter- and intragranular part of the sample has emerged. By taking the temperature corresponding to the crossover between the two contributions at the different DC fields, the intergranular and intragranular response has been separated. Successively, the temperature has been fixed to 77 K, together with an AC frequency equal to 1597.9 Hz, and the χ1″ as a function of the DC field at different AC amplitudes has been analyzed showing a clear presence of granularity in all the curves. By drawing the contour plot of the χ1″ with the DC and AC values, it was possible to determine the best parameters to put at 77 K in order to exploit the material for applications.

Effects of Mn and Ru substitutions on the electrical properties and AC susceptibility of Tl(BaSr)CaCu2O7 superconductor

In this paper, the effects of M = Mn and Ru substitutions at the Tl site of Tl[Formula: see text]Mx(BaSr)CaCu2O7 (Tl-1212) on the electrical properties and AC susceptibility were investigated. The X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) methods were used to examine the phase and microstructure, respectively. All samples showed diffraction patterns with Tl-1212 as the major phase and an increase in the Tl-1223 phase with increasing Mn and Ru substitutions. The microstructure showed partial melting and randomly oriented grains in all samples. The electrical resistance measurements showed metallic normal state behavior for all samples. The zero-resistance transition temperature [Formula: see text] was the highest for x = 0.4 where [Formula: see text] was 107[Formula: see text]K and 90[Formula: see text]K for Mn and Ru substitutions, respectively. The superconducting transition, [Formula: see text] obtained from AC susceptibility measurements increased with Mn and Ru substitutions up to x = 0.4. Using Bean’s model, the current density at the peak temperature of the imaginary part of the AC susceptibility, [Formula: see text]([Formula: see text] was determined to be between 16 and 22[Formula: see text]A[Formula: see text]⋅[Formula: see text]cm[Formula: see text] for Mn, and between 15 and 19[Formula: see text]A[Formula: see text]⋅[Formula: see text]cm[Formula: see text] for Ru-substituted samples. Mn substitution showed a higher transition temperature compared with Ru. This study showed that optimization of the average Cu valence was achieved with Mn and Ru substitutions for x = 0.4 at the Tl site. The ionic radii of the substituting and substituted elements are important factors in enhancing the transition temperature of Tl(BaSr)CaCu2O7 superconductor.

Physical properties of MnFeAl-based alloys affected by Mn content and annealing

The present study is devoted to the Mn2.4Fe0.8Al0.8 and Mn2FeAl alloys prepared by induction melting and studied in their original and subsequently annealed states. The annealing was carried out at 773 K/100 h and 1073 K/100 h in the argon atmosphere. The microstructure, phase composition, magnetic properties, and atom arrangement are followed with regard to Mn content and annealing conditions.The scanning electron microscopy completed by the energy dispersive X-ray spectroscopy and neutron activation analysis has detected single-phase alloys with compositions close to the nominal ones. Their structure, analyzed by X-ray diffraction, was found to be primitive cubic β-Mn with the lattice parameters of 0.6359(2) nm for Mn2.4Fe0.8Al0.8 and 0.6339(1) nm for Mn2FeAl. The coherent potential approximation calculations and positron annihilation spectroscopy have allowed obtaining an overview to the arrangement of Mn, Fe, and Al atoms in the β-Mn structure and formation of the open volume defects. It is shown that Mn atoms occupy predominantly 8c Wyckoff sites and remaining Mn, Fe and Al atoms occupy 12d sites in equal 1/3 proportion. The open volume defects, vacancies and vacancy clusters, occur in both alloys and both annealed states in a very low concentration. From the magnetic viewpoint, both alloys in the as-prepared state and after annealing at 773 K/100 h are paramagnetic at room temperature with transition to antiferromagnetic state at about 30-40 K. The ac susceptibility measurements have indicated spin glass nature of the Mn2FeAl alloys. The annealing at a higher temperature, 1073 K/100 h, has affected mainly Mn2.4Fe0.8Al0.8 alloy manifesting a weak ferro-/ferrimagnetic contribution at room temperature contributing to a strong magnetic ordering below 42 K.

Magnetic Anisotropy and Relaxation in Four-Coordinate Cobalt(II) Single-Ion Magnets with a [CoIIO4] Core.

A mononuclear four-coordinate Co(II) complex with a [CoIIO4] core, namely, PPN[Li(MeOH)4][Co(L)2] (1) (PPN = bis(phosphoranediyl)iminium; H2L = perfluoropinacol), has been studied by X-ray crystallography, magnetic characterization, and theoretical calculations. This complex presents a severely distorted coordination geometry. The O-Co-O bite angle is 83.42°/83.65°, and the dihedral twist angle between the O-Co-O chelate planes is 55.6°. The structural distortion results in a large easy-axis magnetic anisotropy with D = -104(1) cm-1 and a transverse component with |E| = +4(2) cm-1. Alternating current (ac) susceptibility measurements demonstrate that 1 exhibits slow relaxation of magnetization at zero static field. However, the frequency-dependent out-of-phase (χ"M) susceptibilities of 1 at 0 Oe do not show a characteristic maximum. Upon the application of a dc field or the dilution with a diamagnetic Zn matrix, the quantum tunneling of magnetization (QTM) process can be successfully suppressed. Notably, after dilution with the Zn matrix, the obtained sample exhibits a structure different from that of the pristine complex. In this altered sample, the asymmetric unit does not contain the Li(MeOH)4+ cation, resulting in an O-Co-O bite angle of 86.05° and a dihedral twist angle of 75.84°, thereby leading to an approximate D2d symmetry. Although such differences are not desirable for magnetic studies, this study still gives some insights. Theoretical calculations reveal that the D parameter is governed by the O-Co-O bite angle, in line with our previous report for other tetrahedral Co(II) complex with a [CoIIN4] core. On the other hand, the rhombic component is found to increase as the dihedral angle deviates from 90°. These findings provide valuable guidelines for fine-tuning the magnetic properties of Co(II) complexes.

Quantum spin liquid ground state in the trimer rhodate Ba4NbRh3O12

Frustrated magnets offer a plethora of exotic magnetic ground states, including quantum spin liquids (QSLs), in which enhanced quantum fluctuations prevent a long-range magnetic ordering of the strongly correlated spins down to lowest temperature. Here we have investigated the trimer based mixed valence hexagonal rhodate Ba4NbRh3O12 using a combination of dc and ac magnetization, electrical resistivity, specific heat, and muon spin rotation/relaxation (μSR) measurements. Despite the substantial antiferromagnetic exchange interactions, as evident from the Weiss temperature (θW∼−35 to −45K), among the Rh-local moments, neither long-range magnetic ordering nor spin freezing is observed down to at least 50 mK, in ac-susceptibility, specific heat, and zero-field μSR measurements (down to 0.26 K). We ascribe the absence of any magnetic transition to enhanced quantum fluctuations as a result of geometrical frustration arising out of the edge-sharing equilateral Rh-triangular network in the structure. Our longitudinal-field μSR result evidences persistent spin fluctuations down to 0.26 K, thus stabilizing a dynamic QSL ground state in Ba4NbRh3O12. Furthermore, the magnetic specific heat data at low T reveal a significant T-linear contribution plus a quadratic T dependence, which may indicate the gapless Dirac QSL phenomenology of the spinon excitations with a linear dispersion. Published by the American Physical Society 2024

Unraveling the origin of the Griffiths phase in Ho2NiMnO6: perspectives from linear and nonlinear AC susceptibility

In this study, we investigated the magnetic ordering and underlying mechanism of the Griffiths phase, observed in Ho2NiMnO6 through AC susceptibility measurements. Our results indicate that the transition around 86 K corresponds to a paramagnetic to ferromagnetic transition characterized by classical magnetic ordering. Notably, nonlinear AC susceptibility measurements revealed the existence of ferromagnetic clusters within a paramagnetic background well above the transition temperature, establishing this as the origin of the Griffiths-like phase within the Ni/Mn sublattice of Ho2NiMnO6. Our study on the Ho2NiMnO6 system provides insight into the intricate magnetic phenomena common to various other strongly correlated electron systems.

Incidence of the Brownian Relaxation Process on the Magnetic Properties of Ferrofluids.

Ferrofluids containing magnetic nanoparticles represent a special class of magnetic materials due to the added freedom of particle tumbling in the fluids. We studied this process, known as Brownian relaxation, and its effect on the magnetic properties of ferrofluids with controlled magnetite nanoparticle sizes. For small nanoparticles (below 10 nm diameter), the Néel process is expected to dominate the magnetic response, whereas for larger particles, Brownian relaxation becomes important. Temperature- and magnetic-field-dependent magnetization studies, differential scanning calorimetry, and AC susceptibility measurements were carried out for 6 and 13.5 nm diameter magnetite nanoparticles suspended in water. We identify clear fingerprints of Brownian relaxation for the sample of large-diameter nanoparticles as both magnetic and thermal hysteresis develop at the water freezing temperature, whereas the samples of small-diameter nanoparticles remain hysteresis-free down to the magnetic blocking temperature. This is supported by the temperature-dependent AC susceptibility measurements: above 273 K, the data show a low-frequency Debye peak, which is characteristic of Brownian relaxation. This peak vanishes below 273 K.

Heptanuclear Mixed-Valence Co4IIICo3II Molecular Wheel─A Molecular Analogue of Layered Double Hydroxides with Single-Molecule Magnet Behavior and Electrocatalytic Activity for Hydrogen Evolution Reactions.

We present a bifunctional heptanuclear cobalt(II)/cobalt(III) molecular complex formulated as [Co7(μ3-OH)4(H2L1)2(HL2)2](NO3)6·6H2O (1) (where H5L1 is 2,2'-(((1E,1'E)-((2-hydroxy-5-methyl-1,3-phenylene)bis(methanylylidene))bis(azanylylidene))bis(propane-1,3-diol)) and H2L2 is 2-amino-1,3-propanediol). Compound 1 has been characterized by single-crystal X-ray diffraction analysis along with other spectral and magnetic measurements. Structural analysis indicates that 1 contains a mixed-valence Co7 cluster where a central Co(II) ion is connected to six different Co centers (four CoIII and two CoII ions) by four μ3-OH groups, giving rise to a planar heptanuclear cluster that resembles a molecular fragment of a layered double hydroxide (LDH). Two triply deprotonated (H2L1)3- ligands form the outer side of the cluster while two singly deprotonated (HL2)- ligands are located at the top and bottom of the central heptanuclear core. Variable temperature magnetic measurements indicate the presence of weak ferromagnetic CoII···CoII interactions (J = 3.53(6) cm-1) within the linear trinuclear CoII cluster. AC susceptibility measurements show that 1 is a field-induced single-molecule magnet (SMM) with τ0 = 8.2(7) × 10-7 s and Ueff = 11.3(4) K. The electrocatalytic hydrogen evolution reaction (HER) activity of 1 in homogeneous phase shows an overpotential of 455 mV, with a Faradaic efficiency of 81% and a TOF of 8.97 × 104 μmol H2 h-1 mol-1.

Signatures of nearly compensated magnetism and spin glass behavior in highly frustrated β-Mn-type Mn50Fe25+xAl25-x Heusler alloys.

The present study examines the effect of Fe/Al concentration on the structural and magnetic properties of Mn-rich Mn50Fe25+xAl25-x (x = 5, 10, 15) Heusler alloys through x-ray diffraction, temperature- and field-dependent DC magnetization, thermoremanent magnetization, magnetic memory effect, AC susceptibility measurements, and DFT calculations. The samples crystallize in a cubic β-Mn structure. The trend shows a reduction in lattice parameters (unit cell volume) with the increasing Fe proportion. These alloys exhibit strong antiferromagnetic interactions with large frustration parameters, indicating the presence of competing magnetic interactions. The DC magnetization data reveal spin glass-like features with a peak at spin glass freezing temperature (Tf). The observation of bifurcation in temperature-dependent zero-field-cooled and field-cooled magnetization curves, exponential dependence of the temperature variation of remanence and coercivity, magnetic relaxation, and magnetic memory effect below Tf support the spin-glass character of these alloys. The frequency dependence of Tf is also examined in the context of dynamic scaling laws, such as the Vogel-Fulcher law and critical slowing down model, which further supports the presence of spin glass behavior. In the theoretical DFT calculations, the electronic structure is found to be metallic and similar for both spin projections. Moreover, the antiferromagnetic arrangement of the magnetic moments, in line with the experimental observations, is stabilized by exchange interactions, resulting in an almost compensated total magnetic moment of 0.02-0.38µB/f.u. This is probably caused by the frustrated structure and non-stoichiometric compositions of Mn50Fe25+xAl25-x.

Experimental studies on noncentrosymmetric Nd3Se4: Strongly correlated noncollinear ferromagnet

We have synthesized polycrystalline Nd3Se4 by the solid state sealed tube reaction route followed by structural characterization and magnetic property measurements. The temperature-dependent magnetization studies reveal the existence of competing magnetic interactions below the ferromagnetic ordering (TC ≈ 48.4 K). The observation of hysteresis in the isothermal magnetization M(H) data with the coercive field of ≈ 0.25 T at 2 K indicates dominant ferromagnetic interactions in the applied field. The nonsaturating behavior of M(H) data at higher applied field and kinks in corresponding dM/dHvs. H plots suggest the coexistence of multiple magnetic interactions at low temperatures. Using the M(T,H=2 T) data, the Rhodes-Wohlfarth ratio (qc/qs) has been estimated to be ≈ 3.6, which supports the itinerant magnetism in Nd3Se4. These competing interactions have been further investigated by AC-susceptibility measurements at various excitation frequencies. The χ′ reduces drastically with an increase in the applied DC field, as observed from isothermal field-dependent AC-χ studies. Additionally, the strong correlation between delocalized charge and localized magnetic moments is evident from ρ(T) measurements at H = 0 and 5 T. The ρ(T,H=0 T) data shows a clear drop having quadratic temperature dependence, below TC. Furthermore, the inter-dependence between electrical transport and magnetism has been established firmly through negative magnetoresistance, in which the maxima correspond to the coercive field obtained from M(H) data.