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The insoluble organic material (IOM) in primitive chondritic meteorites is very enriched in D (up to δD ≈ 3500‰ in bulk). Based largely on a series of electron paramagnetic resonance (EPR) studies of IOM from three meteorites (Orgueil, Murchison and Tagish Lake), it has been suggested that these enrichments are the result of exchange with H2D+ in the solar nebula and that exchange with radicals in the IOM was particularly facile so that they are enormously enriched in D (δD ≥ 95000‰). To try to test whether radicals are largely responsible for the D enrichments in IOM, we have used EPR to measure the radical concentrations (spins/g) and g-factors of 18 IOM separates from C1-2 chondrites of varying petrologic type and chemical group that have a much wider range of H isotopic compositions (δD ≈ 600–3500‰) than in previous studies. We confirm the previous studies findings that IOM exhibits non-Curie law behavior and that it does not completely saturate even at microwave excitation powers of 200 mW. We also have obtained similar g-factor values. However, our IOM samples typically exhibit a lower and more limited range of spin concentrations, and smaller deviations from Curie law behavior than in previous studies. Nor do we observe correlations between bulk δD and either spins/g or non-Curie law behavior that would be expected if exchange between H2D+ and radicals, as previously proposed, was the cause of the D-enrichments in IOM. Indeed, in general the radical concentrations and the degree of non-Curie law behavior do not seem to correlate with any of the measured IOM properties, with chondrite group or parent body history (e.g., degree of aqueous alteration). The only exceptions are the IOM in four Tagish Lake lithologies whose spin concentrations increase with increasing degree of thermal processing as indicated by decreasing H/C and δD, and increasing aromaticity.

Partially reduced graphene oxide (prGO) obtained by hydrothermal reduction was studied by electron paramagnetic resonance (EPR) spectroscopy in the temperature range 4.2–300 K. The EPR absorption is accompanied by nonresonant microwave absorption due to dielectric and conduction losses in prGO. This additional absorption is taken into account to determine correctly intensities of EPR spectra. The EPR spectra of prGO consist of the broad and narrow components. Above 100 K, the intensity of the broad component exhibits the Curie-Weiss behavior, but below 100 K it follows the Curie law revealing the disappearance of antiferromagnetic correlations. For the first time, the unusually strong increase of the narrow EPR signal intensity with lowering temperature is observed. This effect is explained by the Anderson localization of conduction electrons in the defected crystalline structure of prGO. Due to low spin density, the localized electrons become isolated and their magnetic susceptibility follows the Curie law with the temperature-dependent number of magnetic moments. Effects of adsorption of atmospheric gases on the observed properties are analyzed.

In this paper, we consider a new method that employs a highly sensitive nuclear magnetic magnetometer with flowing water to determine the magnetic susceptibility and Curie constant of magnetic fluids with an error no greater than 1.0%. The Curie law was shown to be fulfilled in the temperature range of 283–323 K, in which ferrofluidic cells are used. A further increase in the temperature of the ferromagnetic fluid leads to an insignificant change in the Curie constant. The results of experimental studies are presented.

A new universal technique was suggested to determine the Curie constant С and magnetic susceptibility of colloidal solutions placed in hermetically sealed vessels (for instance, ferrofluid cells) with an error of no more than 1.0%. Experimental research demonstrated that in the temperature range Т from 283 to 323 K, in which ferrofluid cells are used, the Curie law is fulfilled. It was established that increase in temperature Т of the colloidal solution from 324 to 363 K in a ferrofluid cell leads to an insignificant increase in С, which needs to be taken into account when conducting experiments using these cells. Results of research on colloidal solutions are presented in the paper.

Pulsed NMR techniques have been used to study the dynamics of $$^3\hbox {He}$$ confined to the interior of the hexagonal nanochannels of MCM-41 for which the walls were coated with a monolayer of $$^4\hbox {He}$$ as determined by isotherm measurements. The $$^3\hbox {He}$$ was added afterward to form a 1D $$^3\hbox {He}$$ line density of about 0.1 $$\hbox {A}^{-1}$$ , corresponding to a Fermi temperature of $$T_{\mathrm{F}} \sim$$ 120 mK. A distinct and appreciable departure from the Curie law was observed for the nuclear spin magnetization below 0.5 K. The temperature dependence of the nuclear spin–lattice relaxation times, $$T_1$$ , for temperatures $$0.05

An electron-spin resonance technique has been used to examine the influence exerted by the degree of compensation on spin effects in a set of nonmagnetic Ge:As semiconductor samples in the vicinity of the insulator–metal phase transition at temperatures 2 K ≤ T ≤ 80 K. It was found that the behavior of the paramagnetic susceptibility, specific to the Pauli paramagnetism and manifested in the spin density resonance, is drawn deep into the insulator state and is observed up to rather large degrees of compensation K ≈ 0.7 at temperature 20 K ≥ T ≥ 5–10 K. Outside this temperature range, both the quantities rapidly grow with increasing compensation and their behavior approaches the Curie law characteristic of the strong insulator state. The reason for this behavior is that the degeneracy is lifted at high temperatures and, at low temperatures, electron states are localized at the Fermi level as a result of the Coulomb blockade by compensating acceptors of the most closely lying donor states and the resulting formation of a narrow Coulomb band in the metallized impurity band. At temperature T ≥ 5–10 K, the gap is blurred by thermal excitations and has no effect on the manifestation of the Pauli paramagnetism. The behavior of the line width of the electron-spin resonance is determined by the scattering on quasi-stationary electric dipoles created by the Coulomb blockade at low temperatures and by the scattering on phonons at high temperatures. The behavior of the g-factor is qualitatively correlated with the specific features of the paramagnetic susceptibility and spin density: with decreasing temperature it weakly grows in the range of the Pauli paramagnetism and then rapidly increases in the range in which the Coulomb blockade is manifested and a transition occurs to the Curie law. By an analogy with ferromagnetic materials in which such a fast increase in the g-factor is observed, the possibility of a compensation caused ferromagnetic coupling of spins localized on donors. The microscopic model of such a coupling is discussed.

The numerical simulation was applied to study the temperature dependence of the impurity magnetic susceptibility. The direct exchange interaction of the impurity magnetic moments randomly distributed in space was considered within the Ising model. When the temperature in a system decreases, the magnetic susceptibility behavior in this system ceases to comply with the Curie law, which is associated with the formation of a spin glass phase. It is shown that the expression of the preexponential factor in the formula for the direct exchange interaction considerably influences the temperature dependence of the magnetic susceptibility only in the case of ferromagnetic exchange.

Bovine spleen has been used as a sample for deep magnetochemical investigation. Temperature dependence of the magnetic susceptibility and field dependence of the magnetization reveal a paramagnetic behaviour that violates the Curie law. The zero-field cooled magnetization and field cooled magnetization experiments show the bifurcation point at ca TC = 20 K and the blocking temperature TB = 10 K confirming a dominating portion of ferritin along with the organic tissue. There is a remnant magnetization at temperature below 20 K and the search for the magnetic hysteresis was positive.

We explain the lambda (λ) transition in the heat capacity in terms of spin freezing on the basis of finite-sized block spin concepts. Thus, the spin-glass phase or the antiferromagnetic/paramagnetic phase near the Neel temperature may be considered as a short-range ordering of the block spins comprised of many random spins with respective majority spin directions. Using the Curie law for the block spins, we obtain the λ-type heat capacity in the lower and the higher temperature approximations of the Brillouin function. The theoretical heat capacity gives a good fit to the experimental data.

Metal oxide photocatalysts TiO2/MoO3 and TiO2/MoO3:V2O5 have been investigated by electron paramagnetic resonance (EPR) spectroscopy under in situ light excitation. Structural identification of all paramagnetic centers (PCs) recorded, such as surface and lattice Ti3+ ions as well as Mo5+ and V4+ ions and nitrogen 14N atoms containing the unpaired electron (“N•-radicals”), have been performed. The temperature behavior of PCs in the range of 30–300 K and photoinduced changes of EPR spectra under light irradiation have been investigated. The validity of the Curie law was confirmed for the PCs of such composite photocatalysts. A new original method of detection of charge carrier separation and accumulation is suggested using EPR-technique. It is shown that TiO2/MoO3 and TiO2/MoO3:V2O5 photocatalysts are capable to accumulate photogenerated charge providing fresh possibilities for practical applications in photocatalysis because these oxide heterostructures retaining oxidation activity for a long time (more than 5 h) under the dark conditions after illumination.

Highly oriented Cr-substituted Ni55Mn34Sn11 Heusler thin films having thickness ~ 400 nm were deposited by Ultrahigh vacuum dc magnetron sputtering on MgO (100) substrates. At room temperature, the films exhibit a mixture of dominant L21 cubic austenite phase, as revealed by the intense (002) and (004) peaks, along with small fraction of the orthorhombic–martensitic phase. Surface morphology of the thin films showed distribution of Cr-rich and Cr-deficit regions together with patterned and aligned magnetic domains, thus bringing out the inherent room temperature ferromagnetism of the film. At temperatures above the Curie temperature, TC ~ 321 K, the magnetic behaviour of the films is seen to follow the Curie law rather than the Curie–Weiss law. Ferromagnetic to antiferromagnetic transition appears at TN ~ 247 K, which gives rise to exchange bias at low temperatures due to the coexistence of the two magnetic orders. This phase coexistence also leads to the formation of a spin glass state deep into the martensitic region. The film exhibits metal-like nature at high temperature and semiconductor-like behaviour with the lowering of temperature. A reentrant metallic state is observed at T ≤ 38 K during cooling that persists up to ≤ 62 K in warming cycle. The hysteresis in the ρ–T curve spread over a very wide temperature range confirms the magnetic phase coexistence in the martensitic state in the present thin films. The magnetoresistance (MR) first increases (2.4% at 300 K and H = 50 kOe) with temperature and maximizes to around ~ 3.25% at T = 150 K and then starts decreasing. Its value in the glassy state is very small. This shows that a magnetic liquid like state is more conducive to larger MR.

The temperature scales of screening of local magnetic and orbital moments are important characteristics of strongly correlated substances. In a recent paper X. Deng et al. using dynamic mean-field theory (DMFT) have identified temperature scales of the onset of screening in orbital and spin channels in some correlated metals from the deviation of temperature dependence of local susceptibility from the Curie law. We argue that the scales obtained this way are in fact much larger, than the corresponding Kondo temperatures, and, therefore, do not characterize the screening process. By reanalyzing the results of this paper we find the characteristic (Kondo) temperatures for screening in the spin channel $T_K\approx 100$ K for V$_2$O$_3$ and $T_K\approx 350$ K for Sr$_2$RuO$_4$, which are almost an order of magnitude smaller than those for the onset of the screening estimated in the paper ($1000$ K and $2300$ K, respectively); for V$_2$O$_3$ the obtained temperature scale $T_K$ is therefore comparable to the temperature of completion of the screening, $T^{\rm comp}\sim 25$ K, which shows that the screening in this material can be described in terms of a single temperature scale., This is a post-peer-review, pre-copyedit version of an article published in Matters Arising section of Nature Communications. The final authenticated version is available online at http://dx.doi.org/10.1038/s41467-021-21641-2

We introduce and study a simplification of the symmetric single-impurity Kondo model. In the Ising-Kondo model, host electrons scatter off a single magnetic impurity at the origin whose spin orientation is dynamically conserved. This reduces the problem to potential scattering of spinless fermions that can be solved exactly using the equation-of-motion technique. The Ising-Kondo model provides an example for static screening. At low temperatures, the thermodynamics at finite magnetic fields resembles that of a free spin-1/2 in a reduced external field. Alternatively, the Curie law can be interpreted in terms of an antiferromagnetically screened effective spin. The spin correlations decay algebraically to zero in the ground state and display commensurate Friedel oscillations. In contrast to the symmetric Kondo model, the impurity spin is not completely screened, i.e., the screening cloud contains less than a spin-1/2 electron. At finite temperatures and weak interactions, the spin correlations decay to zero exponentially with correlation length $\xi(T)=1/(2\pi T)$., Comment: 26 journal pages, 15 figures

In the Kitaev honeycomb model, the quantum spin fractionalizes into itinerant Majorana and gauge flux spontaneously upon cooling, leading to rich experimental ramifications at finite temperature and an upsurge of research interest. In this work, we employ the exponential tensor renormalization group approach to explore the Kitaev model under various perturbations, including the external fields, Heisenberg, and the off-diagonal couplings that are common in the Kitaev materials. Through large-scale manybody calculations, we find a Kitaev fractional liquid at intermediate temperature that is robust against perturbations. The fractional liquid exhibits universal thermodynamic behaviors, including the fractional thermal entropy, metallic specific heat, and an intermediate-temperature Curie law of magnetic susceptibility. The emergent universal susceptibility behavior, with a modified Curie constant, can be ascribed to the strongly fluctuating $\mathbb{Z}_2$ fluxes as well as the extremely short-ranged and bond-directional spin correlations. With this insight, we revisit the susceptibility measurements of Na$_2$IrO$_3$ and $\alpha$-RuCl$_3$, and find evident signatures of finite-temperature fractionalization and ferromagnetic Kitaev couplings. Moreover, the peculiar spin correlation in the fractional liquid corresponds to a stripy structure factor which rotates in the extended Brillouin zone as the spin component changes. Therefore, our findings encourage future experimental exploration of fractional liquid in the Kitaev materials by thermodynamic measurements and spin-resolved structure factor probes., Comment: 16 pages, 16 figures

An in situ electrochemical electron paramagnetic resonance (EPR) spectroscopic study of N-doped reduced graphene oxide (N-rGO) is reported with the aim of understanding the properties of this material when employed as an electrical double-layer capacitor. N-rGO shows a capacitance of 100 F g−1 in 6 M KOH, which is twice that found for reduced graphene oxide (rGO). The temperature dependence of the rGO EPR signal revealed two different components: a narrow component, following the Curie law, was related to defects; and a broad curve with a stronger Pauli law component was attributed to the spin interaction between mobile electrons and localised π electrons trapped at a more extended aromatic structure. The N-rGO sample presented broader EPR signals, indicative of additional contributions to the resonance width. In situ EPR electrochemical spectroscopy was applied to both samples to relate changes in unpaired electron density to the enhanced capacitance. The narrow and broad components increased and diminished reversibly with potential. The potential-dependent narrow feature was related to the generated radical species from corresponding functional groups: e.g. O- and N-centred radicals. Improved capacitance seen for the N-modified basal graphene planes can be accordingly suggested to underlie the enhanced capacitance of N-rGO in basic electrolytes.

The Cryogenic Sapphire Oscillator is today recognized for its unprecedented frequency stability, mainly coming from the exceptional physical properties of its resonator made in a high quality sapphire crystal. With these instruments, the fractional frequency measurement resolution, currently of the order of 1e-16, is such that it is possible to detect very small phenomena like residual resonator environmental sensitivities. Thus, we highlighted an unexpected magnetic sensitivity of the Cryogenic Sapphire Oscillator (CSO) at low magnetic field. The fractional frequency sensitivity has been preliminary evaluated to 1e-13/Gauss, making this phenomenon a potential cause of frequency stability limitation. In this paper we report the experimental data related to the magnetic sensitivity of the quasi-transverse magnetic Whispering Gallery (WGH) modes excited in sapphire crystals differing from their paramagnetic contaminants concentration. The magnetic behavior of the WGH modes does not follow the expected theory combining the Curie law and the Zeeman effect affecting the Electron Spin Resonance of the paramagnetic ions present in the crystal., 7 pages,10 figures, to be submitted to PRB

The AC magnetic susceptibility in the range 5–130 K of the tellurite glass systems: TeO2–MnO2–ZnO–PbO and TeO2–MnO2–V2O5–Fe2O3 was measured and analyzed. The investigations of the AC magnetic susceptibility facilitated the determination of the molar susceptibility, paramagnetic magnetic susceptibility, paramagnetic Curie temperature, and magnetic entropy changes of the tellurite glasses. The results clarified that the temperature dependence of the magnetic susceptibility deviated from the Curie law and the increase of the small negative values of Curie temperature indicated negative interchange interactions between the antiferromagnetically coupled manganese ions within the present glass network. The magnetic moments evaluated from susceptibility measurements of the glasses show the predominance of the Mn2+ valence state than Mn3+ valence state of MnO2.

First-principles calculations have been performed to study elastic, electronic, thermodynamic, transport and superconducting properties of recently reported osmium based two superconductors, XOsSi (X = Nb, Ta). We have calculated elastic constants and elastic moduli of XOsSi compounds for the first time. The calculated values of bulk, Young's, shear moduli are slightly larger than the average value obtained from the rule of mixtures of the constituents. NbOsSi and TaOsSi both compounds are found to be relatively hard material, elastically stable and ductile in nature. The obtained directional bulk modulus and shear anisotropic factors indicate that both compounds have high elastic anisotropy. The shear anisotropic factors show higher elastic anisotropy than the percentage anisotropy in these compounds. The Debye temperature and bulk modulus increases with pressure but decreases with temperature as usual for metals. The magnetic susceptibility (χ) of TaOsSi follows the Curie law but NaOsSi does not follow due to its delocalized magnetic moment and electronic specific heat (c) slightly deviates from the linear relationship with temperature. The calculated band structures of XOsSi compounds exhibit metallic nature. In both cases, d-orbitals have the dominating contribution to the total density of states. The smaller electron-phonon coupling constant implies that XOsSi (X = Nb, Ta) are weakly coupled superconductors.

We report structural, magnetic and temperature dependent dielectric properties of diluted magnetic semiconductor Zn0.90Ni0.05Mn0.05O prepared by solid state reaction technique. X-ray diffraction analysis revealed formation of single phase hexagonal wurtzite structure. Scanning electron microscopy and atomic force microscopy images indicated increase in grain size and roughness respectively with increasing sintering temperature. Field dependent DC magnetization at low temperature exhibited ferromagnetic ordering with coercivity ~ 6 × 104 A/m and remanence ~ 17 A/m. Complex initial permeability values were found to be positive for the measurement frequency range (1 kHz–120 MHz) with a relaxation at lower frequency. Temperature dependent DC magnetization and AC susceptibility followed curie law with curie temperature below 65 K. Temperature dependent dielectric constants ($$\varepsilon ^{\prime}\,\& \,\varepsilon ^{\prime\prime}$$) and loss tangents ($$tan\delta$$) measured for selected frequencies were found to be an increasing function of temperature and decreasing function of frequency. AC conductivity ($${\sigma }_{ac}$$) values were found to be an increasing function of frequency and temperature. Clear signatures of relaxations were observed in $$\varepsilon ^{\prime},\,\varepsilon ^{\prime\prime},$$ $$tan\delta$$ and $${\sigma }_{ac}$$ for temperatures above 200 °C.

In this paper, we study the effect of the signal-to-noise ratio of magnetization measurements on the determination of the Curie temperature from the analysis of the magnetocaloric response. The procedure has been compared with the method of the inflection point of the magnetization versus temperature curves. Magnetization data have been simulated using the Arrott–Noakes equation of state, with the addition of different noise levels (either 1% of the measured signal or 0.3% of the measurement range). It is shown that the obtained values of the Curie temperature are more accurate in the case of the magnetocaloric procedure, although this method requires more data analysis than the inflection point method. Moreover, the field independence of the Curie temperature obtained from the magnetocaloric procedure allows us to perform a statistical analysis of the obtained values, reducing the associated error in the Curie temperature determination.

Dielectric and magnetic properties of SrTi 1 − x Fe x O 3 were measured for a single crystal sample ( x =0.0032) and a ceramic sample ( x =0.02). Temperature dependences of the dielectric constants were analyzed on the basis of a Vendik's formula, which describes a quantum paraelectric state accurately. A small amount of Fe impurities in the single crystal does not affect the characteristic temperatures of the dielectric properties, but does affect the quality of the crystal. This change in quality causes a large change in the dielectric constant of the quantum paraelectric state. The temperature dependence of the dielectric constant of the quantum paraelectric state of the ceramic sample is different from that of the single crystal not only quantitatively, but also qualitatively. The magnetic susceptibilities obey the typical Curie law, though a deviation of the Curie law was observed below 5 K for x =0.02. Crystals with the both concentrations remain in paramagnetic states at 2.5 K. The magnetic properties of SrTi 1 − x Fe x O 3 can, in all likelihood, be explained by the orientation effect of free Fe 3 + ions. In addition, an antiferroelectric interaction suggested for EuTiO 3 by an analysis of dielectric constants based on a Barrett's formula was turned out to be unnecessary following analysis of the same data based on the Vendik's formula.

The temperature dependence of magnetic susceptibility χ (Τ), 78 59.634) decreases to a minimum for sample x=0.6. Highest resistivity (ρ) and ac susceptibility (χ) are observed for x=0.6. Metal- semiconductor transition temperature Tρ decreases gradually with Mg doping, in contrast to ferromagnetic-paramagnetic Curie temperature Tc which shows weak dependence on Mg doping level. Low temperature resistivity showed upturn in the temperature range 28–37 K. At high temperatures, variable range hopping conduction predominates with density of states N(Ef) ~3×1019−6×1019 (eV−1 cm−3). Low temperature resistivity follows ferrometallic nano-particle relation: ρ=ρo +ρ1T2 +ρ2T4.5. AC susceptibility of x=0.0 and 0.6 fit well to Curie law, samples x=0.2, 0.4, 0.8 and 1.0 are better described in the framework of Neel ferrimagnetism. Transport and magnetic susceptibility results are interpreted in terms of core-shell model where ferromagnetic core interacts anti-ferro-magnetically with ferromagnetic shell.

Using full-potential local-orbital minimum-basis along with spin-polarized relativistic Korringa-Kohn-Rostoker methods, we study the electronic, Fermi surface, Curie temperature and optical properties of Zr2CoAl alloy. The alloy with Li2AgSb and Cu2MnAl structures are compared in terms of magnetic properties, and the electronic structures in two structures are also discussed. According to the calculated electronic states, it finds that the Zr2CoAl with Li2AgSb structure is half-metallic ferromagnet with an integral magnetic moment of 2.00 μ B , meanwhile we also notice the d-d and p-d hybridizations are responsible for the formation of minority-spin gap, furthermore, the fat-bands are applied to discuss the mixture between d and p electrons in the vicinity of the Fermi level. The Fermi surfaces related to the valence bands are constructed, and it is found that the spin-up valence bands 26, 27 and 28 across the Fermi energy dominate the nature of electrons. By mapping the system onto a Heisenberg Hamiltonian, we obtain the exchange coupling parameters, and observe that the Zr(A)-Co(C) and Zr(A)-Zr(B) interactions provide a major contribution for exchange interactions. Based on the calculated exchange coupling parameters, the Curie temperature is estimated to be 287.86 K at equilibrium, and also the dependence of Curie temperature on lattice constant related to the tunable Curie temperature in Zr2CoAl alloy is studied. Finally, we report the optical properties of Zr2CoAl alloy, and present the photon energy dependence of the absorption, the optical conductivity and the loss function.

Using the spin-polarized relativistic Korringa-Kohn-Rostoker method, we study the exchange interactions and Curie temperatures of Fe 2 Ni Z ( Z = Al, Ga, Si, Ge) with the Hg 2 CuTi structure. The Heisenberg exchange coupling parameters and Curie temperatures are obtained by calculating the exchange interactions between the constituents. It is found the nearest neighbor exchanges play a leading role in interactions, the calculated Curie temperatures, which are higher than the room temperature, decrease when changing Z from III to IV group. In addition, we study the influence of lattice constant on magnetic moments and Curie temperatures. It is found the Fe magnetic moments become more larger due to the reduction of atomic orbital overlap as the expansion of lattice parameters. Only small changes are observed for the moment of Ni atom, while for the Z atom, the magnetic moment is nearly constant. Finally, the Curie temperatures of Fe 2 Ni Z compounds under different lattice constants are acquired by using the mean-field approximation.

The magnetization of noninteracting metallic nanoparticles is investigated by comparing the particle-size and temperature dependences of the magnetization for several mechanisms. The nanoparticle magnetization deviates from that of the underlying bulk materials due to zero-temperature and thermal effects, and on a mean-field level, the corresponding surface-core interaction is described by a Landau–Ginzburg approach. A major factor is the reduced atomic coordination at the surface, which has often, but not always, opposite effects on the zero-temperature magnetization and Curie temperatures. The coordination effect is particularly pronounced for very weak itinerant ferromagnets and for strongly exchange-enhanced Pauli paramagnets. With regard to external magnetic fields, the nanoparticle magnetization involves several “superparamagnetic” phenomena, namely, Neel relaxation, Brownian relaxation, and Langevin macrospin paramagnetism.

The nuclear magnetization of 3He adsorbed by the nanostructured material MCM-41 with a channel size of 2.5 nm was investigated using the pulse nuclear magnetic resonance method. The amplitude of the spin-echo signal was measured in the experiment after the application of two probe pulses to the system. The resulting temperature dependence of the signal magnitude, for various 3He coatings, is described by common dependence corresponding to the Curie law. It is demonstrated that the values of the echo signal amplitude determined in the experiment coincide with the calculated value of the corresponding amplitude due to nuclear magnetization that arises in the system of 3He nuclear spins in an external magnetic field.The nuclear magnetization of 3He adsorbed by the nanostructured material MCM-41 with a channel size of 2.5 nm was investigated using the pulse nuclear magnetic resonance method. The amplitude of the spin-echo signal was measured in the experiment after the application of two probe pulses to the system. The resulting temperature dependence of the signal magnitude, for various 3He coatings, is described by common dependence corresponding to the Curie law. It is demonstrated that the values of the echo signal amplitude determined in the experiment coincide with the calculated value of the corresponding amplitude due to nuclear magnetization that arises in the system of 3He nuclear spins in an external magnetic field.

We report Raman-scattering results of YbRu$_2$Ge$_2$ single crystals to explore the phononic and crystal-field (CF) excitations. This heavy-fermion metal is suggested to enter a ferroquadrupolar (FQ) phase below T$_0$=10 K. The tetragonal CF potential splits the Yb$^{3+}$ $^2F_{7/2}$ ground multiplet into two $\Gamma_6$ and two $\Gamma_7$ Kramers doublets. We establish the following CF level scheme of the ground multiplet: a $\Gamma_6$ ground state, with the two $\Gamma_7$ states at 2 cm$^{-1}$, 95 cm$^{-1}$ and the other $\Gamma_6$ state at 239 cm$^{-1}$. The $\sim$2 cm$^{-1}$ separation between the CF ground and first excited states is in agreement with the previously proposed quasi-quartet CF ground state. The intensity of the lowest-energy CF transition remarkably increases on cooling, indicating a coupling of this CF excitation to the quadrupolar fluctuations above T$_0$. From symmetry analysis, we suggest that the FQ order has B$_{1g}$ symmetry. Moreover, temperature-dependent study of four Raman-active phonon modes shows that the intensities of the A$_{1g}$ and one E$_{g}$ modes increase significantly on cooling, which is explained by a near-resonant coupling between these two phonon modes and CF transitions.

Electron paramagnetic resonance (EPR) spectroscopy is used to address the remarkable persistence of the native Arrhenius dependence of the 2-aminopropanol substrate radical rearrangement reaction in B(12)-dependent ethanolamine ammonia-lyase (EAL) from Salmonella typhimurium from physiological to cryogenic (220 K) temperatures. Two-component TEMPOL spin probe mobility in the presence of 10 mM (0.08% v/v) 2-aminopropanol over 200–265 K demonstrates characteristic concentric aqueous-cosolvent mesodomain and protein-associated domain (PAD, hydration layer) solvent phases around EAL in the frozen solution. The mesodomain formed by the relatively small amount of 2-aminopropanol is highly confined, as shown by an elevated temperature for the order–disorder transition (ODT) in the PAD (230–235 K) and large activation energy for TEMPOL rotation. Addition of 2% v/v dimethylsulfoxide expands the mesodomain, partially relieves PAD confinement, and leads to an ODT at 205–210 K. The ODT is also manifested as a deviation of the temperature-dependence of the EPR amplitude of cob(II)alamin and the substrate radical, bound in the enzyme active site, from Curie law behavior. This is attributed to an increase in sample dielectric permittivity above the ODT at the microwave frequency of 9.5 GHz. The relatively high frequency dielectric response indicates an origin in coupled protein surface group–water fluctuations of the Johari–Goldstein β type that span spatial scales of ∼0.1–10 Å on temporal scales of 10(−10)–10(−7) s. The orthogonal EPR spin probe rotational mobility and solvent dielectric measurements characterize features of EAL protein–solvent dynamical coupling and reveal that excess substrate acts as a fluidizing cryosolvent to enable native enzyme reactivity at cryogenic temperatures.

We herein propose an alternative phenomenology to explain the phase of proton glass by reference to finite block spin theory in magnetism, in which the phase may be considered as being a short-range ferroelectric ordering of block pseudo-spins comprised of random pseudo-spins that have a majority of individual pseudo-spins in a given sense. By making use of the Curie law of block pseudo-spins, we obtained the dielectric susceptibility for the lower and higher temperature approximations of the Brillouin function . The experimental results for the susceptibility in hydrogen-bonded mixed crystals of ferroelectric RbH 2 P(As)O 4 and antiferroelectric NH 4 H 2 P(As)O 4 were thus fitted fairly well at low temperatures in the proton glass phase whereas some deviation from our formulation was seen at high temperatures in the paraelectric phase.

A new method of determining the thermodynamic temperature of colloid solutions placed onto a sealed glass vessel is considered; the method is based on measurements of the magnetic susceptibility in flowing liquid by the magnetic nuclear resonance method. Experimental results show that the Curie law holds for colloid solutions in the temperature range of 278–333 K, in which ferrofluid cells prepared based on these solutions are used.

The magnetic properties of nonstoichiometric lanthanum manganites La1–x Mn1–y O3 have been studied in the temperature range 80 K < T < 650 K. The Curie temperature T C changes nonmonotonically as the number of Mn4+ ions increases. In the paramagnetic region, there exist isolated Mn ions and magnetic polarons which can be conserved to T ⩽ 4T C, independent of the lattice symmetry. In the T C < T < T pol region, the temperature dependences of the magnetic susceptibility are nonlinear and can be described by the Curie law with a temperature-dependent Curie constant C. The sample has been prepared having a composition near the O′ → O structural transition; the spontaneous magnetization of the sample at T ⩽ 1.6T C is associated to correlated polarons forming due to the double exchange in chains of the E-type antiferromagnetic phase.

Based on the dynamic spin-fluctuation theory, we study the spin-density correlations in the ferromagnetic metals. We obtain computational formulae for the correlation function and correlation radius in different approximations of the theory. Using these formulae, we calculate the magnetic short-range order above the Curie temperature in bcc Fe. Results of the calculation confirm our theoretical prediction that the inverse correlation radius increases linearly with temperature for T sufficiently large. The calculated short-range order is small but sufficient to correctly describe neutron scattering experiments. A considerable amount of the short-range order is shown to persist up to temperatures much higher than the Curie temperature.

Specific magnetic and magneto-thermal properties of Er2Fe14Si3, in the temperature range of 80–300 K, have been investigated using basic laws of classical statistical mechanics in a simple model. In this model, the constructed partition function was used to derive, and therefore calculate the temperature and/or field dependence of a host of physical properties. Examples of these properties are: the magnetization, magnetic heat capacity, magnetic susceptibility, probability angular distribution of the magnetization vector, and the associated angular dependence of energy. We highlight a correlation between the energy of the system, its magnetization behavior and the angular location of the magnetization vector. Our results show that Er2Fe14Si3 is an easy-axis system in the temperature range 80–114 K, but switches to an easy-plane system at T≥114 K. This transition is also supported by both of the temperature dependence of the magnetic heat capacity, which develops a peak at a temperature ~114 K, and the probability landscape which shows, in zero magnetic field, a prominent peak in the basal plane at T=113.5 K.

Pyroelectric coefficients are measured for Si, Sr, La, Al, and Gd doped HfO2 thin films as well as the solid-solution Hf0.5Zr0.5O2 composition from 280 to 440 K. Pyroelectric currents show sensitivity to the dopant used to stabilize ferroelectricity in HfO2. Large pyroelectric coefficients up to 70 μC cm−2 K−1 were measured in films with the largest remanent polarization magnitudes, La-doped HfO2 and Hf0.5Zr0.5O2. A temperature-driven ferroelectric to antiferroelectric-like transition influences the pyroelectric coefficient and is found only in Si-doped HfO2 thin films. The transition is shown to produce a decrease in the Curie constant with temperature and thus deviates from the Curie law, although most ferroelectric films reported here obey the Curie law. Independent measurements of the remanent polarization, relative permittivity, and pyroelectric coefficient are used to extract the Curie constants of the thin films. The fundamental thermodynamic relationship between the dielectric, ferroelectric, and pyroelectric properties of ferroelectric HfO2 thin films are established based on Landau theory with a universal Curie constant of 5.8 × 10−7 ± 0.46 × 10−7 K C V−1 m−1 (Landau coefficient, α0 = 1.72 × 106 ± 0.138 × 106 V m K−1 C−1) for ferroelectric HfO2 independent of doping concentration and dopant type. An electro-thermal coupling factor of 1.9 × 10−3 and a voltage responsivity figure of merit of 0.085 m2/C illustrate the promising potential of ferroelectric HfO2 thin films for use in embedded energy harvesting and infrared sensing circuits.

En el presente trabajo se utilizó el código Wien2k, en el marco de la teoría del funcional de la densidad de Kohn-Sham, aplicando el método de ondas planas aumentadas y linealizadas (full-potential linearized augmented plane wave, FP- LAPW) y adoptando la aproximación de gradiente generalizado (GGA) de Perdew, Burke y Ernzerhof para la energía de intercambio y correlación, así como la aproximación de densidad local (local density approximation, LDA) para el cálculo de la densidad de estados y la estructura de bandas de la perovskita doble Sr2HoNbO6. Para los cálculos se consideró el grupo Fmm (#225), experimentalmente obtenido a partir de mediciones de difracción de rayos X y del método de refinamiento de Rietveld. El parámetro de red experimental fue de 8.018 Å, el cual concuerda en un 99,2 % con las predicciones teóricas efectuadas a partir de la minimización de la energía mediante la ecuación de estado de Murnaghan. A partir de mediciones de susceptibilidad magnética en función de la temperatura y del ajuste con la ley de Curie, se obtuvo el valor del momento magnético efectivo 10,01 μB. Este valor es muy cercano del esperado teóricamente a partir de las reglas de Hund (10,60 μB). La brecha de energía determinada entre las bandas de valencia y de conducción fue de 3,3 eV, lo que revela el carácter aislante de la perovskita compleja Sr2HoNbO6 para la configuración de espín hacia arriba, en tanto que se observó el carácter semiconductor para la polarización de espín hacia abajo, con una brecha de energía de 0,77 eV. Las propiedades termodinámicas se calcularon a partir de la ecuación de estado usando el modelo cuasi-armónico de Debye. Un comportamiento del calor específico, con CV≈CP, se encontró a temperaturas inferiores a T = 500 K, con valores del límite de Dulong-Petit que doblaban los que se han reportado para materiales del tipo de la perovskita. In this work we used the Wien2k code, within the framework of the Kohn-Sham Density Functional Theory (DFT), applying the Full-Potential Linearized Augmented Plane Wave method (FP-LAPW) and adopting the Generalized Gradient approximation (GGA) for the exchange-correlation energy due to Perdew, Burke, and Ernzerhof, as well as the Local Density approximation (LDA) for the calculation of the Density of States and band structure of the Sr2HoNbO6 double perovskite. For calculations, we considered the Fmm (#225) space group, which was experimentally obtained from X-ray diffraction measurements and Rietveld refinement. The experimental lattice parameter was 8.018 Å, which is 99.2% in agreement with the theoretical prediction from the minimization of energy through the Murnaghan state equation. From the measurements of magnetic susceptibility as a function of temperature and the adjustment with the Curie law, we obtained a value for the effective magnetic moment of 10.01 μB, which is close to the theoretical expected from Hund’s Rule (10.60 μB). An energy gap of 3.3 eV between the valence band and the conduction band revealed the insulator character of the Sr2HoNbO6 complex perovskite for the spin up configuration, but a semiconductor feature was observed for the spin down polarization, with an energy gap of 0.77 eV. The thermodynamic properties were calculated from the state equation by using the Debye quasiharmonic model. A specific heat behavior of CV≈CP was found at temperatures below T = 500 K, with Dulong-Petit limit values doubling those reported for perovskite materials.

Multistimuli responsive soft materials are urgently needed in many different fields, such as anticounterfeiting technology and microdroplet manipulation. Herein, the straightforward preparation of fluorescigenic magnetofluids by the introduction of the paramagnetic metal ions Gd3+, Tb3+, and Dy3+ into alkylimidazolium-based ionic liquids (ILs) is reported. Bright visible fluorescence was observed under UV irradiation for Tb- and Dy-containing ILs. Either pure samples or papers coated with these ILs exhibited pronounced magnetic responses. Consistent and stable structures of these salts were confirmed by systematical characterizations. Because of the competition of nitrate ligands, structural water in the precursors was eliminated easily under a vacuum. For Tb- and Dy-containing ILs, featured electronic transitions were observed and were assigned in the fluorescence spectra. The long lifetimes of these transitions were also confirmed. The field-cooling experiments showed that all of these ILs display paramagnetism at room temperature. At low temperature, small deviations from the Curie Law indicate the occurrence of antiferromagnetic coupling and spin canting in these ILs. Temperature-induced differences in magnetic properties were further verified by field-dependent magnetic susceptibility measurements carried out at 5 and 300 K.

Iron borate FeBO 3 is an excellent example of the materials called “transparent magnets” [1], associating room temperature magnetic ordering (weak ferromagnetism) with transmission windows in visible spectral range [2]. The persisting research interest in iron borate is stimulated by its outstanding magnetic, magneto-acoustical, optical, magneto-optical, resonance, etc. characteristics [3–7]. Recently, new iron borate-based materials - Fe x Ga 1-x BO 3 crystals - have been synthesized by the solution in the melt technique [8] and studied by Electron Paramagnetic Resonance (EPR) [9], Nuclear Magnetic Resonance [10, 11] as well as by optical and magnetooptical techniques [12]. These crystals: (i) per se possess extraordinary physical characteristics suitable for practical applications, and these characteristics can be monitored in the synthesis process; (ii) allow comprehensive studies of diamagnetic dilution - isomorphous substitution of iron by gallium - effect on the properties of magnetic materials, viz., gradual transition from magnetically ordered to paramagnetic state; (iii) allow understanding the nature of various mechanisms responsible for magnetic properties of iron borate, e.g., magnetocrystalline anisotropy, the former having different concentration and temperature dependences. Different types of Electron Magnetic Resonance (EMR) have been observed in Fe x Ga 1-x BO 3 crystals depending on iron contents and the temperature. Figure 1 (a) shows the spectra transformation with x. At x = 1 (pure iron borate), only a low-field resonance is observed, earlier identified as Antiferromagnetic Resonance (AFMR) [7]. At a lower iron content, x = 0.75, besides the low-field line a new broad resonance emerges at higher magnetic fields, with the effective g-factor g≈2. Since iron substitution for gallium occurs more or less randomly, such crystals are expected to contain regions with different local iron concentrations, implying different magnetic ordering. The low-field line observed in the mixed crystals, by analogy with iron borate [7], can be identified as AFMR line arising from magnetically ordered regions, whereas the high-field line can be ascribed to Cluster Magnetic Resonance (CMR), i.e., EMR arising from only partially magnetically ordered regions. Both the low- and highfield EMR lines are present in all crystals with 0.35 ≤ x < 1; thus, one can conclude that in such crystals both long-range and short-range (cluster-type) magnetic ordering coexist. Figure 1 (b) shows the temperature dependence of the CMR line intensity for x = 0.65. With decreasing temperature this line considerably broadens and its intensity does not follow the T−1 Curie law, confirming its attribution to magnetic clusters. At still lower iron contents, x = 0.2, the AFMR line disappears and the high-field line increases in intensity. The EMR spectra for x = 0.2 crystal consist of a single line at g≈2, quite similar to the high-field line observed for higher x, consequently, in this case the antiferromagnetic regions are absent in the whole temperature range. The temperature dependence of the intensity of this line shown in Figure 1 (c), confirms that the Curie law for this resonance is not respected. For x = 0.04, the latter line also disappears and the EPR spectrum of diluted Fe3+ ions, broadened by dipole-dipole interactions, comes into view. At a still lower iron content, x = 0.003, this spectrum is spectacularly narrowed. A detailed account of the EPR studies of these crystals has been recently carried out using laboratory-developed codes [9]. In order to confirm or infirm the existence of magnetic clusters in the mixed iron-gallium borates, we have carried out SQUID measurements. The temperature dependence of the magnetic susceptibility in crystals with intermediate x-values, e.g., see Figure 2, reveals the presence of a strong out-of-phase component, thereby confirming the existence of magnetic clusters at intermediate x values. Acknowledgments This work was partially supported by the V.I. Vernadsky Crimean Federal University Development Program for 2015 – 2024.

Post-mortem electron paramagnetic resonance spectroscopy experiments have been carried out between room temperature and 20 K to examine the radiation-induced defects in fictive temperature (Tf) treated Heraeus F300 silica (0.1 ppm OH, 1500 ppm Cl2). In particular, we focus our attention on Self-Trapped Hole (STH) centers detected in 1000 °C, 1100 °C, and 1200 °C Tf treated samples irradiated at room temperature by gamma rays at 6 kGy. By repeating annealing cycles between 77 and 300 K on the same samples, we observed that the EPR signal attributed to STH decreases as the temperature increases but in a reversible manner. We evidenced a deviation from the Curie law for T > 70 K and suggested an interpretation based on the decrease in the “strain-assisted TH” population by reversible excitation of the trapped hole to a delocalized state with an activation energy of 7.8 meV. This also means that the precursors of hole trapping sites (a local strain atomic configuration) remain stable until 300 K at least.

The ε-Fe2O3 nanoparticles in borate glasses co-doped with low concentrations of Fe2O3 and Gd2O3 were investigated with two experimental techniques – visible magnetic circular dichroism (MCD) and electron spin resonance (ESR). The most prominent features of the MCD spectra are: non-linear dependence of the spectral maxima intensities on the Gd concentration and strong increase with the temperature decrease. The ESR spectra of these glasses exhibit two features with g = 4.3 due to the diluted Fe3+ ions and 2.0 associated both with Fe3+ ions and with nanoparticles. The integrated spectra intensities do not follow the T-1 Curie law suggesting a considerable contribution from the magnetically ordered nanoparticles to ESR. Analysis of the MCD and ESR concentration dependences allow suggestion on the Gd ions incorporation into nanoparticles.

Post-mortem EPR spectroscopy has been carried out to examine the radiation-induced Self-Trapped Hole (STH) in fictive temperature (Tf) treated Heraeus F300 silica. By repeating isochronal annealing cycles between 77 and 300 K, we observed that STH decreases with T but in a reversible manner. We evidenced a deviation from the Curie law for T > 70 K and suggest an interpretation based on the decrease of a “strain-assisted Trapped Holes” population by a reversible excitation of the trapped hole to a delocalized state with activation energy of 7.8 meV.