Spin state and exchange in the quasi-one-dimensional antiferromagnet KFeS2

We report the optical spectra and single crystal magnetic susceptibility of the one-dimensional antiferromagnet KFeS₂. Measurements have been carried out to ascertain the spin state of Fe³⁺ and the nature of the magnetic interactions in this compound. The optical spectra and magnetic susceptibility could be consistently interpreted using aS=1/2 spin ground state for the Fe³⁺ ion. The features in the optical spectra have been assigned to transitions within thed-electron manifold of the Fe³⁺ ion, and analysed in the strong field limit of the ligand field theory. The high temperature isotropic magnetic susceptibility is typical of a low-dimensional system and exhibits a broad maximum at ∼565K. The susceptibility shows a well defined transition to a three dimensionally ordered antiferromagnetic state atT _N=250 K. The intra and interchain exchange constants,J andJ′, have been evaluated from the experimental susceptibilities using the relationship between these quantities, andχ _max,T _max, andT _N for a spin 1/2 one-dimensional chain. The values areJ=−440.71 K, andJ′=53.94 K. Using these values ofJ andJ′, the susceptibility of a spin 1/2 Heisenberg chain was calculated. A non-interacting spin wave model was used belowT _N. The susceptibility in the paramagnetic region was calculated from the theoretical curves for an infiniteS=1/2 chain. The calculated susceptibility compares well with the experimental data of KFeS₂. Further support for a one-dimensional spin 1/2 model comes from the fact that the calculated perpendicular susceptibility at 0K (2.75×10⁻⁴ emu/mol) evaluated considering the zero point reduction in magnetization from spin wave theory is close to the projected value (2.7×10⁻⁴ emu/mol) obtained from the experimental data.     

Magnetism,exchange and crystal field parameters in the orbitally unquenched Ising antiferromagnet FePS3

FePS₃ is a layered antiferromagnet (T _N=123 K) with a marked Ising anisotropy in magnetic properties. The anisotropy arises from the combined effect of the trigonal distortion from octahedral symmetry and spin-orbit coupling on the orbitally degenerate⁵ T _2g ground state of the Fe²⁺ ion. The anisotropic paramagnetic susceptibilities are interpreted in terms of the zero field Hamiltonian, ℋ=Σ_i [δ(L _iz ² −2)+|λ|L _i .S _i ]−Σ _ij J _ij S _i .S _j . The crystal field trigonal distortion parameter Δ, the spin-orbit coupling λ and the isotropic Heisenberg exchange,J _ij, were evaluated from an analysis of the high temperature paramagnetic susceptibility data using the Correlated Effective Field (CEF) theory for many-body magnetism developed by Lines. Good agreement with experiment were obtained for Δ/k=215.5 K; λ/k=166.5 K;J _nn k=27.7 K; andJ _nnn k=−2.3 K. Using these values of the crystal field and exchange parameters the CEF predicts aT _N=122 K for FePS₃, which is remarkably close to the observed value of theT _N. The accuracy of the CEF approximation was also ascertained by comparing the calculated susceptibilities in the CEF with the experimental susceptibility for the isotropic Heisenberg layered antiferromagnet MnPS₃, for which the high temperature series expansion susceptibility is available.     

Magnetically two-phase state in Eu1−x AxMnO3 (A=Ca, Sr)

It is observed that low-temperature magnetic properties (dependence of the magnetization on the cooling conditions and the presence of a maximum in the initial magnetic susceptibility) of Eu_{1− x} A_xMnO₃ (A=Ca, Sr; x=0,0.3) samples are similar to those of spin glasses. However, there are also substantial differences: The magnetization depends on the cooling conditions right up to the maximum measurement fields H=45 kOe, and the temperature of T _N of the maximum of the initial magnetic susceptibility is independent of the frequency of the ac magnetic field in which the susceptibility is measured. The magnetization isotherms for T<T _N are a superposition of a linear part, characteristic for an antiferromagnet, and a small spontaneous part. For compositions containing Sr a maximum of the resistivity ρ (ρ_max∼10⁸ Ω ·cm) is observed near T _N; in a 120 kOe magnetic field this maximum is lowered by four orders of magnitude and the temperature of the maximum is two times higher. In compositions with x=0.3 the paramagnetic Curie point is much higher than for the composition with x=0: θ=110 K (A=Ca), 175 K (A=Sr), and −100 K (x=0). These characteristic features of the magnetic and electric properties are explained by the existence of a magnetically two-phase state in this system, consisting of ferromagnetic clusters, in which the charge carriers are concentrated, embedded in an insulating antiferromagnetic matrix. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 5, 375–380 (10 March 1999)     

Quantum Monte Carlo investigation of the 2D Heisenberg model with S=1/2

The two-dimensional (2D) Heisenberg model with anisotropic exchange (Δ = 1−J _x /J _z ) and S=1/2 is investigated by the quantum Monte Carlo method. The energy, susceptibility, specific heat, spin-spin correlation functions, and correlation radius are calculated. The sublattice magnetization (σ) and the Néel temperature of the anisotropic antiferromagnet are logarithmic functions of the exchange anisotropy: 1/σ+1+0.13(1)ln(1/Δ). Crossover of the static magnetic structural factor as a function of temperature from power-law to exponential occurs for T _c /J≈0.4. The correlation radius can be approximated by 1/ξ=2.05T ^1.0(6)/exp(1.0(4)/T). For La₂CuO₄ the sublattice magnetization is calculated as σ=0.45, the exchange is J=(1125–1305) K; for Er₂CuO₄ J∼625 K and the exchange anisotropy Δ∼0.003. The temperature dependence of the static structural magnetic factor and the correlation radius above the Néel temperature in these compounds can be explained by the formation of topological excitations (spinons). Fiz. Tverd. Tela (St. Petersburg) 41, 116–121 (January 1999)     

Magnetic and structural correlations in EuMnO and BiMnO crystals in the paramagnetic temperature range

The magnetic and dielectric properties of EuMn₂O₅ and BiMn₂O₅ crystals are investigated over a wide range of temperatures 4.2–250 K, including the range T≫T _N ≃40 K. Significant departures from the Curie-Weiss law are observed in both crystals for the magnetic susceptibility in the paramagnetic range; they are attributed to the presence of correlated domains of magnetic order over a wide range of temperatures. Anomalies in the dielectric properties of the crystals are observed in the same temperature range T>T _N and, as in the case T<T _N , are correlated with the magnetic properties. Zh. éksp. Teor. Fiz. 112, 284–295 (July 1997)     

Nonequilibrium paramagnetic susceptibility of gallium impurity centers in lead telluride

The temperature dependences of the resistance and magnetic susceptibility are studied in gallium-doped lead telluride, which is characterized by a delayed photoconductivity effect, under various illumination conditions. After a sample is illuminated at low temperatures, the magnetic susceptibility is diamagnetic in the region of metallic delayed conductivity (for T<=0 K). In the region of thermodynamic equilibrium (T<70 K), where conductivity is activational, the magnetic susceptibility is likewise diamagnetic and essentially equals the low-temperature value. A paramagnetic susceptibility peak is observed in the transitional region (T∼50–70 K), where the conductivity is of a nonequilibrium character but the carriers are still nondegenerate. This peak increases in magnitude with the rate of measurements in the indicated temperature range. In addition, a paramagnetic variation of the susceptibility following the Curie law is observed with uncontrollable (weak) illumination from the cryostat cap at low temperatures (T<25 K). The interpretation of the observed dependences is based on notions of variable valence of gallium in lead telluride, while the appearance of a paramagnetic susceptibility peak is attributed to the presence of shallow localized levels of gallium in a trivalent state. Zh. éksp. Teor. Fiz. 114, 1859–1867 (November 1998)     

Exchange interactions and spin dynamics in a [CuNd2(C4O4)4(H2O)16]·2H2O crystal

Crystalline [CuNd₂(C₄O₄)₄(H₂O)₁₆]·2H₂O constructed of complexes of trivalent neodymium and divalent copper, has been synthesized and studied by EPR. The square anion groups (C₄O₄) enter as bridge ligands, forming chains of neodymium ions interconnected by (C₄O₄)Cu(C₄O₄) fragments. It is found that the relaxation rate of the neodymium subsystem at room temperature significantly exceeds the exchange interaction rate between copper and neodymium ions. Under these conditions the magnetic properties of the crystal are determined by two magnetically nonequivalent chains of copper ions, which do not interact. The intrachain exchange interaction via hydrogen bonds is estimated to be ∼0.1 cm⁻¹. As one proceeds from the high-temperature (250<T<300 K) to the low-temperature region (T<40 K), a substantial change in the nature of the interaction is revealed. An unusual magnetic structure given in a crystal is observed at low temperatures, which is determined by the presence of two magnetically nonequivalent “ribbons,” formed by the interacting copper and neodymium ions: chains of copper ions are framed on two sides by chains of neodymium ions. The magnitude of the parameter of the exchange interaction between the copper and neodymium ions is estimated as J ^Cu-Nd⩾0.2 cm⁻¹. An exchange interaction between magnetically nonequivalent neodymium ions is not revealed in the EPR spectra. Fiz. Tverd. Tela (St. Petersburg) 39, 2057–2061 (November 1997)     

Modeling a dimer state in CuGeO3 in the two-dimensional anisotropic Heisenberg model with alternated exchange interaction

The two-dimensional Heisenberg spin-1/2 model with alternated exchange interaction along the c axis and an anisotropic distribution of the exchange interaction in the lattice, J _b/J _c=0.1, is examined. A quantum Monte Carlo method is used to calculate the phase diagrams of the antiferromagnet, the dimer state in a plane, the value of the alternation δ of the exchange interaction, and the anisotropy Δ=1−J ^xy/J ^z of the exchange interaction, Δ∼δ ^0.58(6). The following characteristics are calculated for Δ=0.25: the dependence of the temperature of the dimer-state-paramagnet transition on the alternation of the exchange interaction, T _c(δ)=0.55(4)(δ−0.082(6))^0.50(3), the singlet-triplet energy gap, and the dependence of the magnetization on the external field for some values of δ. The value of the exchange interaction, J _c=127 K, the alternation of the exchange interaction, δ=0.11J _c, and the correlation radius along the c axis, ξ _c≈28c, are determined. Finally, it is found that the temperature dependence of the susceptibility and the specific heat are in good agreement with the experimental data. Zh. éksp. Teor. Fiz. 112, 2184–2197 (December 1997)     

Characteristic features of the magnetic ordering of Dy3+ ions in a monoclinic RbDy(WO4)2 single crystal

The investigation of the specific heat of a RbDy(WO₄)₂ single crystal at temperatures 0.2–2.5 K and in magnetic fields up to 2 T are reported. The temperature dependence of the specific heat near T _N=0.818 K is compared with the predictions for different models. The 2D Ising model describes satisfactorily C(T) below T _N, while for T>T _N none of the theoretical models agree with the behavior of C(T) of RbDy(WO₄)₂. The H-T phase diagram for H∥c is complicated and possesses a triple point, where regions of existence of three magnetic phases converge. The magnetic ordering is analyzed from the standpoint of the Jahn-Teller nature of the structural phase transitions occurring in RbDy(WO₄)₂ at higher temperatures. It is shown that the form of the phase diagram depends on the direction of the vector H, for the general case of an arbitrary direction of H, two phase transitions can occur with increasing field. Fiz. Tverd. Tela (St. Petersburg) 41, 491–496 (March 1999)     

Magnetocaloric effect in antiferromagnetic Dy3Co compound

Magnetic properties and magnetocaloric effects (MCEs) of the Dy₃Co compound are studied. Two successive magnetic transitions: the antiferromagnetic (AFM)-to-AFM transition at T _AF =29 K and the AFM-to-paramagnetic (PM) transition with increasing temperature at the Néel temperature T _N =44 K are observed. Dy₃Co undergoes a field-induced metamagnetic transition from the AFM to the ferromagnetic (FM) state below T _N , giving rise to a large MCE. The maximal value of magnetic entropy change ΔS _m is −13.9 J/kg K with a refrigerant capacity (RC) of 498 J/kg around T _N for a field change of 0–5 T. A sign change of MCE in Dy₃Co with magnetic field and temperature is observed near the critical field where the metamagnetic transition occurs.     

Weak exchange interactions in the heteronuclear crystal CuPr2(CCl3COO)8·6H2O

The new heteronuclear crystal CuPr₂(CCl₃COO)₈·6H₂O, constructed of chains containing copper and praseodymium atoms, has been synthesized and investigated by EPR at 9.3 GHz at temperatures ranging from room temperature down to 10 K. At temperatures T∼300–130 K, EPR spectra are observed which are characteristic of isolated polyhedra of copper ions with g _z=2.330±0.005, g _x,y =2.053±0.005, A _z=139×10⁻⁴ cm⁻¹, and A _x,y <26×10⁻⁴ cm⁻¹. At temperatures T<130 K a complex spectrum is observed, associated with the appearance of weak exchange interactions between the copper ions in the chain (J _Cu-CuΣS _i·S _i+1), comparable in magnitude with the hyperfine interactions J _Cu-Cu=0.015 cm⁻¹ at T=10 K. The magnitude of the exchange interaction decreases smoothly as the temperature is raised. It is conjectured that orbitals of the praseodymium ions participate in the process of indirect exchange between the copper ions. Fiz. Tverd. Tela (St. Petersburg) 41, 2154–2157 (December 1999)     

Synthesis and magnetic properties of Cu3B2O6 single crystals

The temperature dependence of the magnetic susceptibility of Cu₃B₂O₆ single crystals grown by spontaneous crystallization from a melt consisting of a mixture of CuO and B₂O₃ and the behavior of their magnetization are investigated in magnetic fields up to 55 kOe. A broad susceptibility maximum is observed near 39 K, and a sharp drop in susceptibility is observed at T<10 K. The paramagnetic Néel temperatures for all orientations of the magnetic field in the crystal investigated are negative, attesting to the predominantly antiferromagnetic character of the exchange interactions. The effective magnetic moment of the Cu²⁺ ion is anisotropic and lies in the range from 1.054μ _B to 1.545μ _B. The magnetization depends linearly on magnetic field at T>10 K, whereas at temperatures below 10 K a discontinuity is observed at fields of the order of 40 kOe. At room temperature, electron magnetic resonance characterized by an almost isotropic g factor (g=2.165) is detected at 36.22 GHz. The exchange interactions in Cu₃B₂O₆ are analyzed on the basis of the Goodenough-Kanamori rules. The possibility of the establishment of a singlet magnetic state in the crystal is analyzed. Fiz. Tverd. Tela (St. Petersburg) 41, 677–679 (April 1999)     

Residual impurity effects on the magnetic ordering in α-Mn observed by hyperfine interaction

We report on the lattice location of indium in and the magnetic ordering of manganese in its α- and β-phases, as seen by perturbed angular correlation. Quadrupole interaction spectra show that indium prefers to replace Mn atoms of type I in α-Mn, but replaces type II atoms in the β-Mn structure. The interaction strength equalseQV _zz /h=3.6 (6) MHz in α-Mn and 172.3 (3) MHz with ν=0.13 (1) in β-Mn. No magnetic ordering down to 4.2 K was observed in β-Mn, while belowT _N =95 K in the α-Mn phase, a magnetic hyperfine interaction appears indicating two distinct magnetic probe environments. The hyperfine field, when measured atT=4.2 K, equals for 70% of the probes 6.33 (1) T, while the remaining fraction senses a 3.10 (4) T field. The magnitudes of the hyperfine fields are essentially unaffected by a variety of conditions in the sample preparation. The ordering temperature, on the contrary, turns out to be rather sensitive to residual impurities especially any oxygen contamination.     

Magnetic susceptibility and inelastic electrical resistivity of GdZnxCu1−x alloys

The deviation from the Nordheim-Kurnakov rule and the anomalous behavior of spin-disordered electrical resistivity in quasi-binary GdZn (T _C =268 K)-GdCu (T _N =142 K) solid solutions is explained in effective medium approximation within percolation theory for the case of three phases, viz., ferro-, antiferro-, and paramagnetic. The strong increase of ρ at zinc concentrations x∼0.45 is attributed to the closeness of the system to the percolation threshold. The phase volumes calculated for the random-distribution case fit well to the concentration dependence of magnetic susceptibility. Fiz. Tverd. Tela (St. Petersburg) 40, 974–979 (June 1998)     

Quenching of the Haldane gap in LiVSi<Subscript>2</Subscript>O<Subscript>6</Subscript> and related compounds

We report results of susceptibility χ and ⁷Li NMR measurements on LiVSi₂O₆. The temperature dependence of the magnetic susceptibility χ(T) exhibits a broad maximum, typical for low-dimensional magnetic systems. Quantitatively it is in agreement with the expectation for an S=1 spin chain, represented by the structural arrangement of V ions. The NMR results indicate antiferromagnetic ordering below T_N=24 K. The intra- and interchain coupling J and J_p for LiVSi₂O₆, and also for its sister compounds LiVGe₂O₆, NaVSi₂O₆ and NaVGe₂O₆, are obtained via a modified random phase approximation which takes into account results of quantum Monte Carlo calculations. While J_p is almost constant across the series, J varies by a factor of 5, decreasing with increasing lattice constant along the chain direction. The comparison between experimental and theoretical susceptibility data suggests the presence of an easy-axis magnetic anisotropy, which explains the formation of an energy gap in the magnetic excitation spectrum below T_N, indicated by the variation of the NMR spin-lattice relaxation rate at T≪T_N.     

Effect of doping on the magnetic properties of the low-dimensional antiferromagnet CuO

The effect of doping with Li⁺, Zn²⁺, Ni²⁺, and Ga³⁺ ions on the magnetic susceptibility of the low-dimensional antiferromagnet CuO (T _N=230 K) has been studied within a broad temperature range of 77–600 K. The solubility of impurity ions in the CuO lattice is low, ⩽3%. Impurity ions, similar to intrinsic defects, distort antiferromagnetic coupling and can shift the long-and short-range magnetic-order regions toward lower T. Fiz. Tverd. Tela (St. Petersburg) 40, 1876–1880 (October 1998)     

Thermal conductivity of crystalline fullerite C60 in the simple cubic phase

The behavior of the thermal conductivity k(T) of bulk faceted fullerite C₆₀ crystals is investigated at temperatures T=8–220 K. The samples are prepared by the gas-transport method from pure C₆₀, containing less than 0.01% impurities. It is found that as the temperature decreases, the thermal conductivity of the crystal increases, reaches a maximum at T=15–20 K, and drops by a factor of ∼2, proportional to the change in the specific heat, on cooling to 8 K. The effective phonon mean free path λ _p, estimated from the thermal conductivity and known from the published values of the specific heat of fullerite, is comparable to the lattice constant of the crystal λ _p∼d=1.4 nm at temperatures T>200 K and reaches values λ_p∼50d at T<15 K, i.e., the maximum phonon ranges are limited by scattering on defects in the volume of the sample in the simple cubic phase. In the range T=25−75 K the observed temperature dependence k(T) can be described by the expression k(T)∼exp(Θ/bT), characteristic for the behavior of the thermal conductivity of perfect nonconducting crystals at temperatures below the Debye temperature Θ (Θ=80 K in fullerite), where umklapp phonon-phonon scattering processes predominate in the volume of the sample. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 8, 651–656 (25 April 1997)     

High-quality YBCO d.c. SQUIDs based on bicrystal substrates

Summary An analysis of superconducting transport properties and magnetic behaviour of d.c. SQUIDs employing YBCO bicrystal grain boundary junctions (GBJs) has been performed. GBJs have been obtained by deposition of ac-axis-oriented YBCO film on a SrTiO₃ bicrystal substrate by ICM sputtering technique. Experimental measurements on a YBCO d.c. SQUID with a misorientation angle θ=20° are reported. The SQUID shows a critical temperatureT _c∼89 K and a high critical current densityJ _c∼3·10⁶ A/cm² atT=4.2 K. Current-voltage characteristics are close to the behaviour predicted by the resistively shunted junction (RSJ) model and the temperature dependenceJ _c(T) shows a linear behaviour at small reduced temperatures and a depressedJ _c value close toT _c. High-quality flux-voltage curves have been found upT=87 K over a large range of magnetic field. The high reproducibility and the good control of transport properties by the variation of θ make YBCO bicrystal GBJs very useful for applications in electronics. Paper presented at the ?VII Congresso SATT?, Torino, 4–7 October 1994.     

Effect of the oxygen excess on the properties of weakly doped La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> lanthanum manganites

The effect of an oxygen excess δ on the magnetic and electrical properties of La_1−x Ca _x MnO_3+δ (x=0.10–0.15) has been studied over wide ranges of temperatures and magnetic fields. As δ increases, the magnetic ordering temperature T_cdecreases by 70–90 K, the magnetoresistance increases (the electrical resistivity decreases by a factor of up to 10⁴ in a field of 9 T), and the effective moment μ_eff of the paramagnetic susceptibility substantially exceeds the theoretical value at temperatures two to four times higher than T _c and undergoes a jump, just as the activation energy of electrical resistivity, at T∼270 K. These results are attributed to the formation of cation vacancies, the localization of electrons in their vicinity with the subsequent formation of magnetic clusters, tunneling (or hopping) of carriers among them, changes in the sizes of clusters with variations in the temperature and magnetic field strength, the onset of frustrations initiated by the competition among different types of exchange interaction, and the dependence of the cluster parameters on the annealing conditions. Annealing of the oxygen-excess samples at high temperatures in vacuum (above 1100°C) restores the samples to a nearly initial state with the magnetic and magnetotransport properties characteristic of weakly doped manganites, as a result of the removal of cation vacancies.     

Spin-assisted photoluminescence of polycrystalline α-MnSe

We have studied photoluminescence of α-MnSe in the antiferromagnetic and paramagnetic phases. Two broad, possibly multi-component emission bands centred at about 1.53 and 1.66 eV are observed at 20 K. The frequencies and intensities of these bands show step-like shift in the vicinity of T_N. On the basis of difference in peak energies at T=1.8 K and T_N the d-p-d superexchange interaction in excited state is estimated to be J_2g(exc)=0.918 meV.