Phase transition studies in CoSiF6·6H2O and Co1−xZnxSiF6·6H2O by Mn(II) EPR

Phase transition studies on single crystals of CoSiF₆·6H₂O and Co_1−xZn_xSiF₆·6H₂O (x = 0.082, 0.182, 0.248) using Mn(II) EPR at X-band were carried out in the temperature range 10–300 K. Phase transitions with considerable thermal hysteresis have been detected in CoSiF₆·6H₂O and Co_1−xZn_xSiF₆·OH₂O (x = 0.082, 0.182). In CoSiF₆·6H₂O, the transition temperatures during cooling (T^c_c) and during heating (T^h_c) were found to be considerably less than those obtained previously from magnetic anisotropy experiments, i.e. 230 and 246 K as against 246 and 259 K. These characteristic temperatures for the dilute crystals having x = 0.082 and 0.182 were 205, 218 K and 175, 185 K, respectively. It is thus evident that magnetic dilution with zinc causes a progressive reduction in the transition temperatures as well as in the thermal hysteresis. The phase transition manifests itself in a large discontinuous increase in the Mn(II) zero-field splitting parameter (D), i.e. from −187 ± 1 G to −290 ± 1 G, in these crystals. The hyperfine coefficient (A) also increases discontinuously from 99 ± 1 G to 102 ± 1 G at T_c. In the dilute crystal with x = 0.248 a very slow continuous decrease in D and practically no change in A have been detected with a lowering of the temperature. A small temperature independent positive g-shift (g = 2.020 ± 0.005) has been observed in all the crystals studied. The spin-lattice relaxation time (T₁) of the Co(II) ion in CoSiF₆·6H₂O at different temperatures, both above and below T_c, has been estimated from the observed Mn(II) hyperfine linewidth. A discontinuous change in T₁ at T_c has been observed. Analysis of the temperature dependence of the linewidth has further revealed that a two-level Orbach process describes well the thermal behaviour of the spin-lattice relaxation of the Co(II) ions in these crystals. The location of the first excited level in CoSiF₆·6H₂O determined from such studies at temperatures both above and below T_c has been examined in the light of the ligand field energy scheme of the Co(II) ion in an octahedral field. It is concluded that the phase transition in this crystal is probably accompanied by a change in sign of the axial field parameter (Δ).     

High-resolution heat capacity of SnCl2·2H2O single crystal

The heat capacity of SnCl₂·2H₂O single crystal was measured in the close vicinity of the phase transition temperature, T_c = 217.994 ± 0.01 K. Its anomalous part ΔC could be expressed as ΔC = A_± ⊥ (T ? T_c)/T_c⊥^-α_±, where α₊ = 0.492 ± 0.02, α_- = 0.492 ± 0.02, A₊ = 1.148 JK^?mol^?, and A_- = 1.155 JK^?mol^?. A quasi-isothermal absorption of the enthalpy amounting to 34 J mol^? was observed at T_c.     

X-ray determination of the linear compressibilities of (SN)x

The linear compressibilities of (SN)_x have been determined up to 22 kbar using a hydrostatic-pressure X-ray cell: at 1 bar, k_a = 5.5;k_b = 2.2; k_c = 5.0; k_[201] = 3.8 —; all in units of 10^-12cm²/dyne. The results are compared with other chain-like solids and confirm the anisotropic three-dimensional bonding character of (SN)_x. Pressure dependence of the electrical conductivity is discussed.     

Microscopic magnetic properties of nonstoichiometric V2O3+x—NMR and inelastic spin-flip neutron scattering measurements

The local magnetic properties of the V sites in the nonstoichiometric V₂O_3+x (0 ? x <0.08) have been examined by nuclear magnetic resonance and inelastic spin-flip neutron scattering techniques. The samples with x = 0.01 and 0.02 show a paramagnetic metal (PM)-antiferromagnetic insulator (AFI) transition. In the AFI phase, two distinct ⁵¹V NMR signals with hyperfine fields H_n = 184.9±0.5 kOe and 71±1 kOe were observed at 1.8 K, which were assigned as due to V³⁺ and V³⁺ sites, respectively. On the other hand, the samples with x = 0.04 and 0.06 were metallic down to 1.4K, and showed a paramagnetic (PM)-antiferromagnetic (AFM) transition at about 10 K. In these samples, a ⁵¹V NMR signal with H_n = 58±2 k0e and one with 〈H_n〉 = 9kOe were observed at 1.8 K, which were assigned as due to V³⁺-like sites and the matrix V sites, respectively. These results are entirely consistent with those obtained from the neutron experiment. We propose that in the metallic phase (0.04 ? x < 0.08) the minority V⁴⁺-like sites are magnetically localized in the delocalized V matrix and may be responsible for the antiferromagnetic long range order below 10 K.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Electron paramagnetic resonance in Y1−cH1.92:Erc

We have investigated the EPR of isotopically enriched ¹⁶⁸Er³⁺ in Y_1?cH_1.92:Er_c where c = 100 and 1400 ppm, at both 1.4 and 9 GHz and between 1.5 and 50 K. Resonance lines were observed from Er³⁺ ions in both sites of cubic symmetry and sites of axial symmetry. We determine the numbers of Er³⁺ in cubic, and C_4v axial symmetry to be in the ratio 2:1. The cubic site resonance line is at g = 6.85 ± 0.07 and is attributed to a Γ₇ doublet. The linewidth has a linear thermal broadening of 3.9 ± 0.05 gauss K^-1 below circa 7 K. From the nonlinear thermal broadening above this temperature we determine the first excited state, in the cubic crystal field scheme, to be a Γ₈ at 35 ± 10 K above the Γ₇ ground state. We have investigated the origins of the (T = 0) residual linewidth for the ions in cubic symmetry, and conclude there to be a small but significant contribution due to unresolved transferred hyperfine structure from the surrounding hydrogen nuclei.     

Transport properties of n-type ferromagnetic semiconductor HgCr2−xInxSe4(x = 0.100)

Measurements of the electrical conductivity, magnetoresistance, and Hall effect were performed on a n-type ferromagnetic semiconductor HgCr_2?xIn_xSe₄(x = 0.100) single crystal from 6.3 to 296 K in magnetic fields up to 1.19×l0⁶A/m. The conductivity decreases rapidly near the Curie temperatureT_c (≈120 K) as the temperature is raised. A large peak in the magnetoresistance is observed near T_c. The Hall effect measurements indicate that the temperature dependence of the conductivity and the magnetoresistance are due mostly to a change in electron mobility. The electron mobility is 1.2 × 10^?2 m²/V · s at 6.3 K, and decreases rapidly near T_c with the rise in temperature. Then it increases slowly from 5.5 × 10^?4 m²/V · s at 160 K to 7.5 × 10^?4 m²/V · s at 241 K. This temperature dependence of the electron mobility can be explained in terms of the spin-disorder scattering which takes into account the exchange interaction between charge carriers and localized magnetic moments.     

Relaxationsphänomene in Mössbauerspektren von Magnetisierten paramagnetischen Substanzen. I [(Fe x,Al1-x )NH4(SO4)2· 12H2O]

The Fe³⁺-spin in alums of type (Fe _x , A1_1-x )NH₄(SO₄)₂ · 12 H₂O interacts (i) with the crystal lattice viaLS-coupling, and (ii) with the spins of the adjacent Fe³⁺-ions via magnetic dipole-dipole interaction. These interactions lead to a time fluctuation of the spin direction, characterized by correlation times τ _c and τ′ _c of increasing order. The times may be deduced from the⁵⁷Fe-Mössbauer spectra of the alums, τ _c from the width, and τ′ _c ≈τ _c from the position of the hyperfine structure lines. The theoretical interpretation of the Mössbauer spectra is relatively simple, when (i) the spin-lattice interaction gets frozen in, and (ii) a strong applied magnetic fieldH _a decouples the spins of the Fe³⁺-ion and the⁵⁷Fe-nucleus. The spectra were taken, therefore, at 4.2 °K and 8 kOe≦H _a ≦ 54 kOe. According to the 1/r ³-dependence of the magnetic dipole-dipole interaction τ _c should be related tox, the Fe-concentration, τ _c ·x≈τ₀=const. Forx≧0.5 our experimental results are in agreement with this rule when τ₀=(1.5±0.5) · 10^?9 s. For an alum withx=0.26, however, the observed spectra cannot be explained in terms of temporal spin fluctuations, at least not in the framework of the models which are available now. Here, presumedly, the electron spins of adjacent Fe³⁺-ions are coupled to more or less isolated and, consequently, relatively stationary spin clusters of various sizes, leading to many time independent internal magnetic fields. A treatment of this proposal is in preparation.     

pp interactions at 303 GeVc: Analysis of diffraction excitation in the reaction pp → pX

The properties of the diffractively excited system observed at low missing mass in the inclusive pp → pX reaction at $\text{303}\text{GeV}\text{c}$ are presented. For diffraction excitation with |x| > 0.9, the cross section, σ_D=(5.6±0.8) mb, the mean charged multiplicity depends on the mass of the diffractive system approximately at 〈n_c〉 ≈ 0.6M_x + 2, and the slope of the momentum transfer distribution with |t| < 0.5 GeV² is 7.5±0.8 GeV^?2.     

An amplitude analysis of ππ scattering from new data on the reaction π−p→π+π−n

We have carried out a partial-wave analysis of ππ scattering in the mass range 1.0 to 2.08 GeV/c². We find solutions similar to those obtained in previous analyses below 1.8 GeV/c² but, in addition, we obtain a new solution which does not suffer from violations of unitarity and is compatible with data from other channels. This solution, when continued to 2.08 GeV/c², shows a g meson with mass and width of 1.734± 0.010 GeV/c²and 0.322±0.035 GeV/c² respectively, and an h meson with mass 1.935±0.013 GeV/c²and width 0.263±0.057 GeV/c². The L = 2 partial wave contains the f meson and an additional resonance with parameters m = 1.502±0.025 Gev/c², Γ = 0.165±0.042 GeV/c²and x = 0.19±0.03. If we associate this state with the f′(1514), our ππ branching fraction is considerably higher than previous determinations. An SU(3) fit to the 2⁺ nonet yields a mixing angle of 38.4± 1.3°.     

ESR identification of a new N2− defect in X-ray irradiated NaN3

A relatively weak ESR spectrum is observed in single crystals of NaN₃ after X-ray irradiation at 77 K. This spectrum, which has an anisotropic g value and exhibits a resolved 5-line hyperfine structure with components in the ratio 1:2:3:2:1, corresponds to a single unpaired electron interacting symmetrically with two spin-one nuclei, in three inequivalent sites. The spin-Hamiltonian parameters are: g_x = 2.0054 ± 0.0005, g_y = 2.0045 ± 0.0005, g_z = 1.9688 ± 0.0005, |A_x| = 4.0 ± 0.2 G, |A_y| = 20.0 ± 0.2 G, and |A_z| = 4.9 ± 0.2 G, c-axis, and y is perpendicular to the c-axis. This spectrum, which is clearly different from that of substitutional N₂^?reported by Gelerinter and Silsbee, is attributed to interstitial N₂^?.     

Phonon coupled cooperative low-spin 1A1high-spin 5T2 transition in [Fe(phen)2(NCS)2] and [Fe(phen)2(NCSe)2] crystals

Heat capacities of [Fe(phen)₂(NCS)₂] and [Fe(phen)₂(NCSe)₂] were measured between 13⁵ and 375 K. A heat capacity anomaly due to the spin-transition from low-spin ¹A₁ to high-spin π₂ electronic ground state was found at 176·29 K for the SCN-compound and at 231·26 K for the SeCN-compound, respectively. Enthalpy and entropy of transition were determined to be ΔH = 8·60 ± 0·14 kJ mol^?1 and ΔS = 48·78 ± 0·71 J K^?1 mol^?1 for the SCN-compound and ΔH = 11·60 ± 0·44 kJ mol^?1 and ΔS = 51·22 ± 2·33 J K^?1 mol^?1 for the SeCN-compound. To account for much larger value of ΔS compared with the magnetic contribution, we suggest that there is significant coupling between electronic state and phonon system. We also present a phenomenological theory based on heterophase fluctuation. Gross aspects of magnetic, spectroscopic, and thermal behaviors were satisfactorily accounted for by this model. To examine closely the transition process, infrared spectra were recorded as a function of temperature in the range 4000 ? 30 cm^?1. The spectra revealed clearly the coexistence of the ¹A₁, and the ⁵T₂ ground states around T_c.     

La–Zn Substituted Hexaferrites Prepared by Chemical Method

La–Zn substituted M-type Ba hexaferrite powders were prepared by sol-gel (Mx) and organometallic precursor (Sk) methods with Fe/Ba ratio of 11.6 and 10.8, respectively. The compositions (LaZn) _x Ba_{1 ? x} Fe_{12 ? x} O₁₉ with 0.0 ≤ x ≤ 0.6 were annealed at 975°C/2 h. The cationic site preferences of nonmagnetic La³⁺ instead of Ba²⁺ ions and Zn²⁺ instead of Fe³⁺ ions were determined by Mössbauer spectroscopy. The La³⁺ ions substitute the large Ba²⁺ ions at 2a site and for x ≥ 0.4 also at 4f₂ site. The nearly all Zn²⁺ ions are placed at the 4f₁ sites. The thermomagnetic analysis of χ(?) confirms that only the small substitutions for x ≤ 0.4 can be taken as a single-phase hexaferrites. The coercivity H _c almost does not change at x = 0.2 for (Mx) samples and further decrease up to x = 0.6. For (Sk) samples at substitution x = 0.2 the values of H _c are decreasing and at higher x the values nearly do not change. The Curie points, T _c, slowly decrease with x for both (Mx) and (Sk) samples.     

Specific heat studies of high-Tc superconductor YBa2Cu3O7−x

Specific heat studies of the high-T_c superconducting compound YBa₂Cu₃O_7−x with bulk transition temperature at 92K are reported. A distinct anomaly of electronic origin in the specific heat is observed with granular-like behavior corresponding to a Sommerfeld constant γ = 7±2mJ(moleCuK²)^±1 Debye temperature (φo ≈ 400K) is obtained by fitting the experimental data with the theoretical Debye specific heat.     

Investigation of the reaction 35Cl(τ, α)34Cl at Eτ = 15 MeV

The ³⁵Cl(τ, α)³⁴C reaction has been used to study the properties of ³⁴Cl levels up to an excitation energy of 5 MeV. Angular distributions of 37 levels were measured with a split-pole magnetic spectrograph, at a bombarding energy of 15 MeV. New levels have been found at 3847, 3964, 4206, 4321 and 4715 keV, all ± 10 keV. There is a strongly excited multiplet at E_x = 5.0 MeV with components at 4939 ± 11, 4958 ± 11, 4971 ± 11, 4998 ± 12 and 5010 ± 13 keV. A DWBA analysis of the α-particle angular distributions yielded l_n values and spectroscopic factors. New spin and parity assignments were obtained. The T = 1 character of the levels at E_x = 4.21 and 4.72 MeV has been determined. Experimental spectroscopic factors are compared with results from recent many-particle shell-model calculations.     

Hall effect and magnetoresistance of (SN)x films

Hall effect and electrical conductivity have been investigated between 77 K and 300 K and the magnetoresistance at 4.2 K for a number of (SN)_x films deposited at substrate temperatures between — 10 and 50°C. The small magnitude of the Hall mobility (? 1 cm² Vsec^?1 at 300 K) and its activated temperature dependence are interpreted in terms of a heterogenous model for (SN)_x films with thin depletion layers separating highly conductive islands. The hole concentration in these islands (p ≈ 10²¹ cm^?3, the microscopic mobility (μ ≈ 500 cm² Vsec^?1 at 4.2 K) and the temperatures dependence of μ are found to be close to values for (SN)_x crystals.     

Crystalline fields,exchange interactions and spin reorientations in TmxHo1−xFe2 systems,studied by a Yb170 Mössbauer probe

Mössbauer studies of the 84.3 keV gamma ray of Yb¹⁷⁰ emitted from Yb in Tm_xHo_1?xFe₂ at various temperatures were performed. These yield the crystalline field parameters (A₄〈r⁴〉 = 36 ± 5 K, A₆〈r⁶〉 = -3 ± 2K, the exchange field (μ_BH_exch = 116 ± 4 K) and the Yb³⁺ free ion hyperfine constants (H_4f = 4100 ± 150 kOe, eqQ = 2400 ± 250 MHz and H (conduction electrons) = 350±100 kOe). Spin relaxation phenomena observed in TmFe₂ at low temperatures give a value of ～ 0.03 for |?(E_F)J_sf|. Spectra observed in Tm_0.2Ho_0.8Fe₂ in the spin reorientation transition region indicate that the transition is of second order.     

The temperature dependence of the angular variation of,and the critical point exponent for the EPR linewidth in the two-dimensional canted antiferromagnetic (C2H5NH3)2MnBr4: Evidence for a structural phase transition

The angular variation of the EPR linewidths in single crystals of (C₂H₅NH₃)₂MnBr₄ has been measured as a function of temperature. The angular dependence is well characterized by δH(θ) = a + b(3 cos²θ ? 1) + c(3 cos²θ ? 1)². The temperature dependence of the expansion coefficients is reported, and the effect of critical point fluctuations near the Néel temperature as well as a linear temperature dependence at high temperature are observed. A sharp decrease in linewidths at 160°K is attributed to a structural phase transition. The Néel temperature is determined to be 46°K (± 1°) from linewidth measurements of a powder sample. The linewidths diverge exponentially near the Néel temperature with a critical point exponent of 1.5.     

High pressure tuning of optical transitions in Mg[Pt(CN)4]·7H2O

Mg[Pt(CN)₄]·7H₂O belongs to the class of tetracyanoplatinates(II) which crystallize in columnar structures. In different M_x[Pt(CN)₄]·yH₂O (MCP) single crystals the in-chain Pt-Pt-distance R varies between 3.67 Å (NaCP) and 3.15 Å (MgCP). Two optical transitions can be observed in polarized emission with the electric field vector E either parallel or perpendicular to the columnar (c)-axis. Polarized emission spectra of MgCP are recorded under hydrostatic pressure up to p ≈ 18 kbar (at 295 K). The transition energy v?₆ can be tuned from 17,600 cm^-1 to about 12,000 cm^-1 (2.18-1.48 eV). The pressure induced red shift for the two transitions is: E 6 c: dv?₆/dp = -320±20 cm^-1/kbar, E ⊥ c: dv?_⊥/dp = -270±20 cm^-1/kbar. These values are discussed in the context of the known functional relationship (for ambient conditions) between v? and R.