H and K spin-lattice relaxation, ionic motion and Raman processes in the proton conducting KHSeO4 single crystal

The spin-lattice relaxation rates of ¹H and ³⁹K nuclei in KHSeO₄ crystals were studied in the temperature range 160-400 K. The spin-lattice relaxation recovery of ¹H nucleus in this crystal can be represented with a single exponential function, and the relaxation T₁⁻¹ curve of ¹H can be represented with the Bloembergen-Purcell-Pound (BPP) function. The relaxation process of ³⁹K with dominant quadrupole relaxation can be described by a linear combination of two exponential functions. T₁⁻¹ for the ³⁹K nucleus was found to have a very strong temperature dependence, T₁⁻¹=βT⁷. Rapid variations in relaxation rates are associated with critical fluctuations in the electronic spin system. The T⁷ temperature dependence of the Raman relaxation rate is shown here to be due to phonon-magnon coupling.     

Exchange interaction and spin dynamics in pentanuclear clusters, Cu3Ln2(ClCH2COO)12(H2O)8 (Ln = Nd3+, Sm3+, Pr3+)

New compounds, [Cu₃Ln₂(ClCH₂COO)₁₂(H₂O)₈]·2H₂O with Ln = Nd³⁺ (I), Sm³⁺ (II), Pr³⁺ (III), built up of pentanuclear clusters were synthesized and studied by means of X-ray analysis and electron paramagnetic resonance (EPR). X-ray data show that all compounds are isostructural and the pentanuclear clusteres may be considered as a linear system with alternating Cu(II) and Ln(III) ions: Cu(2)-L¹-Ln-L²-Cu(1)-L²-Ln-L²-Cu(2) with L¹ and L² being bridging fragments and Cu(1) and Cu(2) being structurally nonequivalent copper complexes. EPR studies demonstrate that in the temperature range of 100–293 K the signals due to only one type of the copper complexes are observed in the spectra of I–III. AtT<100 K the spectral temperature dependence is nontrivial. AtT<30 K new signals are detected in the spectra of I and II. The temperature dependence of the EPR spectra is interpreted under the assumption that the parameter of the exchange interaction Cu(2)-Ln considerably exceeds the parameter of the interaction Cu(1)-Ln. EPR spectra are calculated for the fragments of five paramagnetic centers in the frames of the model taking into account the nonequivalence of two copper complexes, short longitudinal and transverse paramagnetic relaxation times of the rare-earth ions at room temperature and the change of the relaxation rates when the temperature decreases. The results of the calculations show that it is possible to obtain information about the interactions in the system on the basis of the analysis of the temperature dependence of the EPR spectra of the central copper complex. The parameter of the isotropic part of the exchange interaction between copper and neodymium ions (for the interaction Cu(2)-Nd) is estimated as about 15 cm⁻¹. A considerable rearrangement of the spin states when the temperature changes is found for all complexes.     

F NMR and EPR study of fluorinated buckminsterfullerene C60F58

Solid state ¹⁹F NMR in the temperature range from 96 to 366 K and room temperature EPR studies of fluorinated buckminsterfullerene C₆₀F₅₈ have been carried out. The temperature dependence of the line width and the spin-lattice relaxation time show hindered molecular motion with the activation energy of ΔE_a=1.9 kcal/mol. Neither phase transition nor random rotation of C₆₀F₅₈ have been obtained. The spin-lattice relaxation rate is strongly affected by the presence of paramagnetic centers, namely, dangling C-C bonds yielding localized unpaired electrons. Such broken bonds are caused by C-C bond rupture in a cage-opened structure of hyperfluorinated species.     

Structure, phase transitions and molecular dynamics in 4-methylpyridinium tetrachloroantimonate(III), [4-CH3C5H4NH][SbCl4]

Crystal structure of the 4-methylpyridinium tetrachloroantimonate(III), [4-CH₃C₅H₄NH][SbCl₄], has been determined at 240 K by X-ray diffraction as monoclinic, space group, P2₁/n, Z=8. Differential scanning calorimetry and dilatometric studies indicate the presence of two reversible phase transitions of first order type, at 335/339 and 233/289 K (cooling/heating) with ΔS=0.68 and 2.2 J mol⁻¹ K⁻¹, respectively. Crystal dynamics is discussed on the basis of the temperature dependence of the ¹H NMR spin-lattice relaxation time T₁ and infrared spectroscopic studies. The low temperature phase transition at 233 K of an order-disorder type is interpreted in terms of a change in the motional state of the 4-methylpyridinium cations. The phase transition at 335 K, probably of a displacive type, is characterised by a complex mechanism involving the dynamics of both the cationic and anionic sublattice. The ¹H NMR studies show that the low temperature phase III is characterised only by the dynamics of the CH₃ groups.     

Spin lattice relaxation in TmNi5 above its curie temperature

The hexagonal compound TmNi₅ was investigated by means of ¹⁶⁹Tm Mössbauer spectroscopy in the temperature range 4–350 K. Above T_c=4.5 K the magnetic hyperfine interactions were found to be governed by paramagnetic relaxation. This behaviour was interpreted in terms of a stochastic spin-down model. The spin lattice relaxation time was found to follow an exponential temperature dependence.     

13C and 1H nuclear spin lattice magnetic relaxation in undoped polyacetylene

Pulsed NMR spin lattice relaxation measurements on ¹³C and ¹H nuclei in undoped trans-polyacetylene have been carried out between 6 and 295 K. The results indicate that the spin lattice relaxation is due to equilibrium fluctuations of the orientational order parameter for the protons while the carbon relaxation can be attributed to their coupling to paramagnetic impurities. In this temperature range no contribution of solitons has been detected in the relaxation mechanisms.     

Magnetic resonance study of the two-dimensional spin diffusion in the Heisenberg paramaget (C18H37NH3)2MnCl4

¹H nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) techniques were employed to study the perovskite-type layered structure compound (C₁₈H₃₇NH₃)₂MnCl₄ undergoing structural phase transitions. The spin relaxation was found to sensitively reflect the two-dimensional electron spin diffusion.     

EPR study of Ce ions in lutetium silicate scintillators Lu2Si2O7 and Lu2SiO5

Two Ce³⁺-doped scintillator crystals, LSO (Lu₂SiO₅:Ce) and LPS (Lu₂Si₂O₇:Ce), are studied by EPR spectroscopy. The analysis indicates that Ce³⁺ substitutes for Lu³⁺ ion in a C₂-symmetry site for LPS and in two C₁-symmetry sites for LSO, with a preference for the largest one, with 6+1 oxygen neighbors. Angular dependence of the EPR spectrum shows that the electronic ground state of Ce³⁺ is different in these two matrices. It is mainly composed of |M_J|=5/2 state in LPS and |M_J|=3/2 state in LSO. The temperature dependence of the linewidth shows a noticeably long spin lattice relaxation time, especially in LPS, which is the result of a stronger crystal field in LPS than in LSO.     

NMR study of the quasi one dimensional conductor K2Pt(CN)4Br0.3 3H2O under pressure

Investigation of spin lattice relaxation time T₁ and NMR line shift of Pt¹⁹⁵ in KCP under hydrostatic pressure are reported in the temperature range between 78 and 300 K up to 20 kbar. At temperature above 120 K, pressure decreases the relaxation rate appreciably.     

Investigation of TmFe4Al8 and DyFe4Al8 by means of 169Tm and 161Dy Mössbauer spectroscopy

We have performed ¹⁶⁹Tm and ¹⁶¹Dy Mössbauer spectroscopy on TmFe₄Al₈ and DyFe₄Al₈. From the temperature dependence of the electric quadrupole splitting of the ¹⁶⁹Tm spectra of TmFe₄Al₈ we have determined the second order crystal field potential V⁰₂ = (100 ± 10) K and the exchange field term g_Jμ_BH_M = (1 ± 1) K. The temperature dependence of the hyperfine field of the ¹⁶¹Dy spectrum of DyFe₄Al₈ gives g_Jμ_BH_M = (15 ± 3) K. With these exchange fields magnetic transition temperatures of the rare earth sublattices were found, which are consistent with experiment. The relaxation behaviour of the Tm sublattice below T_N = 187 K is discussed.     

Relation between the EPR linewidths and the exchange integrals in ACrO2 (A = Li, NaandK)

The temperature dependence of the peak-to-peak EPR linewidth (ΔH_p-p) of the ACrO₂ (A = Li, Na, K) compounds in the X-band is typical for the previously observed antiferromagnetic interactions. All three oxides show a single absorption line with a lorentzian shape. As expected the room temperature values of ΔH_p-p in the Q-band are very close to those obtained in the X-band. Using the Anderson-Weiss model for exchange-narrowed Lorentzian lines and the high-temperature limit values for ΔH_p-p 's of all three oxides it was possible to estimate the coefficient relating the exchange integrals between the adjacent Cr³⁺-ions in the cationic sublattice to the corresponding exchange fields and the coefficient relating the crystal-field parameters of Cr³⁺-ions to the second moments of the spectral lines.     

嵌段共聚物溶致液晶相中水的2H-NMR动力学分析

采用D₂O 的²H-NMR线型和弛豫分析了PEO-PPO-PEO/D₂O/对二甲苯体系的层状和六角液晶相的动力学行为. 通过实验测得了两个不同体系的自旋 晶格弛豫时间T₁、自旋-自旋弛豫时间T₂和²H-NMR 谱. ²H-NMR 谱均为具有四极劈裂的粉末谱线型，且在谱图的中心，β_LD=54.7°时存在一个倒峰. 倒峰的出现直接表明引起体系中弛豫的主要动力学过程处于极窄化区域. 采用NMR弛豫模型，通过调节动力学参数，使理论模拟的²H-NMR谱、弛豫时间、倒峰的大小与实验的对应量相吻合，求得了体系的动力学参数.     

A study of 3He-4He tunneling motion in solid 3He-4He mixtures by means of T1ϱ measurements

³He spin relaxation time in the rotating frame (T_1?) has been measured for 2% ³He in ⁴He solid samples of different molar volume at exchange plateau region (0.5 K). From the data, the characteristic frequency by which a ³He atom exchanges its position with a neighboring ⁴He atom is determined.     

Sign of the electric field gradient at 57Fe nuclei in Eu3Sc2Fe3O12 garnet

The ⁵⁷Fe Mössbauer effect in conjunction with an external magnetic field H_ext has been used to measure the signs of quadrupole coupling constants Δ at the octahedral (a) and tetrahedral (d) iron sites in the Eu₃Sc₂Fe₃O₁₂ garnet. It is shown that application of H_ext to the sample at temperatures T above the Néel temperature T_N slows down the relaxation effects, whose influence on the spectra depends upon the temperature difference T-T_N. By comparing a spectrum measured at 203.0 K and in H_ext=62.4 kOe with theoretical spectra computed for different combinations of Δ(a), Δ(d) signs, it is concluded that Δ(d) is negative. The sign of Δ(a) could not be determined.     

Magnetic field effect on the critical EPR-dynamics of the cubic ferromagnets CdCr2Se4 and CdCr2S4

We present measurements of the critical behaviour of the EPR linewidths at frequencies 9.21 and 35.5 GHz. In the exchange critical region above T_c (4πx ? 1) the strong field dependence of the linewidths is observed, even when the field variation of susceptibility x is small. This phenomenon is explained by the spin diffusion effect on the linewidth. The spin diffusion coefficients D for CdCr₂Se₄ and CdCr₂S₄ are determined from the linewidths data. The temperature dependence D is found to be consistent with the predictions of the dynamical scaling theory.     

Frequency (field) dependent NMR relaxation rate in the interrupted metallic strand model

We calculate the nuclear magnetic resonance rate T^?1₁ arising from the electron-nuclear hyperfine contact interaction, within the interrupted metallic strand model. The electron levels are assumed to have an energy half width Γ and a mean spacing Δ₀ and it is assumed that all segments have the same nuclear spin temperature. In the limit Γ ? Δ₀, T^?1₁ has nearly the same behaviour for kT ? Δ₀ and kT?Δ₀. It is proportional to temperature but has a Lorentzian magnetic field dependence with halfwidth H= Γ/μ_B. At low fields it is enhanced over the value for a normal metal by the factor Δ₀/Γ.This anomalous behaviour arises from the suppression of electron spin flip processes by a magnetic field and should always occur when electronic states are localised, that is when there is a locally discrete electron energy spectrum. Therefore it may be relevant not only to certain linear chain conductors but to other cases of electron localisation.The present model provides an additional possible source of frequency dependence of T₁ in linear chain materials. In certain materials especially those containing defects, it may be more appropriate than the currently accepted mechanism which involves electron spin diffusion in one dimension.     

Biquadratic exchange interaction between Ru5+ ions in (Ru2O9) clusters

The energy levels of a Ru₂O₉ cluster have been calculated, including a higher order spin interaction. The Ru⁵⁺-Ru⁵⁺ coupling is described by the Hamiltonian ?= -2JS₁· S₂ ?j(S₁·S₂)². The temperature dependence of the magnetic susceptibility is used to determine the values of the bilinear J and biquadratic j exchange integrals: J/k = -161K and j/k = 6.6K. The second term in the Hamiltonian corresponds to a fourth order perturbation involving low spin states.     

Spin autocorrelation of Ni in K2Mn0.975Ni0.025F4 studied by nuclear spin-lattice relaxation

From the nuclear spin-lattice relaxation of the out-of-layer ¹⁹F nuclei in magnetic fields perpendicular to the c-axis the low-frequency component of the autocorrelation function 〈S^z(t)S^z(O)〉 of Ni in ordered K₂Mn_0.975Ni_0.025F₄ is found to be substantially reduced relative to the Mn host. The experimental rates vs temperature are in accord with those for relaxation involving two spin excitations calculated with local Green's functions.     

Frequency dependence of ionic conductivity and dielectric relaxation studies in Na3H(SO4)2 single crystal

Electrical impedance measurements of Na₃H(SO₄)₂ were performed as a function of both temperature and frequency. The electrical conductivity and dielectric relaxation have been evaluated. The temperature dependence of electrical conductivity reveals that the sample crystals transformed to the fast ionic state in the high temperature phase. The dynamical disordering of hydrogen and sodium atoms and the orientation of SO₄ tetrahedra results in fast ionic conductivity. In addition to the proton conduction, the possibility of a Na⁺ contribution to the conductivity in the high temperature phase is proposed. The frequency dependence of AC conductivity is proportional to ω^s. The value of the exponent, s, lies between 0.85 and 0.46 in the room temperature phase, whereas it remains almost constant, 0.6, in the high-temperature phase. The dielectric dispersion is examined using the modulus formalism. An Arrhenius-type behavior is observed when the crystal undergoes the structural phase transition.