199Hg and63,65Cu NMR studies of mercury based high-T c superconductors

Hg-oxide ceramic high temperature superconductors were studied by¹⁹⁹Hg and^63,65Cu NMR spectroscopy. Room temperature spectra, spin-spin and spin-lattice relaxation times of samples with different superconducting transition temperatures are presented. A spin-lattice relaxation time ofT ₁=35 msec and a spin-spin relaxation time ofT ₂=1.6 msec were found for the¹⁹⁹Hg NMR. All samples exhibit similar characteristic powder spectra caused by an axially symmetric¹⁹⁹Hg spin interaction. The isotropic value and the anisotropy of the tensor relative to solid HgCl₂ as a standard substance is estimated. Furthermore, results of^63,65Cu NMR measurements at a temperature of 4.2 K which exhibit a typical powder line shape (forI=3/2) are presented.     

Hindered rotation of CH3 groups and phenyl ring in clofibric acid (drug) studied by35Cl-NQR and1H-NMR spectroscopy

The³⁵C1-NQR frequency (V_Q), nuclear quadrupole spin-lattice relaxation time (T_1Q),¹H-NMR second moment (M ₂), nuclear magnetic spin-lattice relaxation time (T ₁) and spin-lattice relaxation time in rotating frame (T _1p ) were measured for polycrystalline clofibric acid (drug) as a function of temperature. Hindered rotation of two dynamically inequivalent methyl groups and the phenyl ring was detected, the relevant activation energies were determined. The rotations are discussed in detail.     

T1 as a function of larmor frequency in solid CH4 at 4.2 K: An experiment on recent theories

The spin-lattice relaxation time T₁ has been measured in partially converted samples at NMR frequencies ranging from 4 to 55 MHz. Results allow to check in detail the existing models for relaxation in solid CH₄.     

H NMR study of the phase transitions of trissarcosine calcium chloride single crystals at low temperature

The ¹H NMR line-width and spin-lattice relaxation time T₁ of TSCC single crystals were studied. Variations in the temperature dependence of the spin-lattice relaxation time were observed near 65 and 130 K, indicating drastic alterations of the spin dynamics at the phase transition temperatures. The changes in the temperature dependence of T₁ near 65 and 130 K correspond to phase transitions of the crystal. The anomalous decrease in T₁ around 130 K is due to the critical slowing down of the soft mode. The abrupt change in relaxation time at 65 K is associated with a structural phase transition. The proton spin-lattice relaxation time of this crystal also has a minimum value in the vicinity of 185 K, which is governed by the reorientation of the CH₃ groups of the sarcosine molecules. From this result, we conclude that the two phase transitions at 65 and 130 K can be discerned from abrupt variations in the ¹H NMR relaxation behavior, and that ¹H nuclei play important roles in the phase transitions of the TSCC single crystal.     

Critical slowing down of fluctuations in p-terphenyl and p-quaterphenyl observed by proton spin-lattice relaxation

The temperature evolution of the proton spin-lattice relaxation time T₁ in p-terphenyl and in p-quaterphenyl around their order-disorder phase transition has been measured. In both cases pretransitional collective fluctuations destroy the high temperature Arrhenius behaviour of the relaxation rate corresponding to a single reorientational jump motion. The spin-lattice relaxation times present then a drastic decrease until the transition temperature (T₀ = 193 K in p-terphenyl, T₀ = 238 K in p-quaterphenyl). This decrease is associated to the critical slowing down of fluctuations. In the low temperature phase the ordering phenomena lead to a sharp drop of the spin-lattice relaxation rate.     

A study of molecular motion and Raman processes in K3H(SO4)2 and KHSO4 single crystals by observation of H and K spin-lattice relaxation

The spin-lattice relaxation rates for ¹H and ³⁹K nuclei in K₃H(SO₄)₂ and KHSO₄ single crystals, which are potential candidate materials for use in fuel cells, were determined as a function of temperature. The spin-lattice relaxation recovery of ¹H can be represented for both crystals with a single exponential function, but cannot be represented by the Bloembergen-Purcell-Pound (BPP) function, so is not related to HSO₄ motion. The recovery traces of ³⁹K, which predominantly undergoes quadrupole relaxation, can be represented by a linear combination of two exponential functions. The temperature dependences of the relaxation rates for ³⁹K can be described with a simple power law T₁⁻¹=αT². The spin-lattice relaxation rates for the ³⁹K nucleus in K₃H(SO₄)₂ and KHSO₄ crystals are in accordance with a Raman process dominated by a phonon mechanism.     

Phase transition and ferroelastic property studied by using the Cs nuclear magnetic resonance in a CsHSO4 single crystal

The ¹³³Cs spin-lattice relaxation time in a CsHSO₄ single crystal was measured in the temperature range from 300 to 450 K. The changes in the ¹³³Cs spin-lattice relaxation rate near T_c1 (=333 K) and T_c2 (=415 K) correspond to phase transitions in the crystal. The small change in the spin-lattice relaxation time across the phase transition from II to III is due to the fact that during the phase transition, the crystal lattice does not change very much; thus, this transition is a second-order phase transition. The abrupt change of T₁ around T_c2 (II-I phase transition) is due to a structural phase transition from the monoclinic to the tetragonal phase; this transition is a first-order transition. The temperature dependences of the relaxation rates in phases I, II, and III are indicative of a single-phonon process and can be represented by T₁⁻¹=A+BT. In addition, from the stress-strain hysteresis loop and the ¹³³Cs nuclear magnetic resonance, we know that the CsHSO₄ crystal has ferroelastic characteristics in phases II and III.     

Electron spin-lattice relaxation in noncommon metals YBa2Cu3Ox and Rb1C60

Using an original modulation technique, the electron spin-lattice relaxation have been investigated in two noncommon metals: YBa₂Cu₃O_x, high-T_c material doped with 1% Gd, and Rb₁C₆₀, linear polymer phase fulleride. In the first case, the Korringa-like temperature dependence of the Gd³⁺ longitudinal relaxation time T₁, is found forx = 6.59 in a wide temperature range 4.2 <T < 200 K, both above and below T_c = 56 K. Atx = 6.95 (T_c = 90 K), the T₁ behavior within 50 <T < 200 K is evidently affected by spin gap opening with the gap value of about 240 K. At 200 K, an unexpected acceleration of the relaxation rate takes place, suggesting some change in the relaxation mechanism. The data are discussed in terms of the Barnes-Plefke theory with allowance made for microscopic separation of the normal and superconducting phases. In Rb₁C₆₀, the evolution of the ESR line and relaxation rates have been studied accurately in the range of the metal-insulator transition (below 50 K). Interpretation is suggested which takes into account breaking down the relaxation bottleneck due to opening of the energy gap near the Fermi surface. The gap value of about 100 cm^?1 is estimated from the analysis of relaxation rates, lineshape and spin susceptibilities.     

Some peculiarities of spin-lattice relaxation of impurity rare-earth ions in crystals caused by the structure defects

The spin-lattice relaxation times for Nd³⁺ ions in yttrium-aluminum garnets (YAG) and for Yb³⁺ ions in CaF₂ in the low-temperature range have been measured. For the first system the temperature dependence of the relaxation rate is determined to a great extent by the method of sample preparation. For samples grow by the method of the horizontally oriented crystallization the dependence is described asT ₁ ^?1 =AT ⁿ ,n ? 4.7, which is an evidence of an influence of local structure disordering on the relaxation. The temperature dependence of the relaxation rate in CaF₂:Yb is also “anomalous”:T ₁ ^?1 =AT ^3.3. The results are compared with the previous data on the relaxation in similar systems, and with other cases of observation of “anomalous” temperature dependences. Different manifestations of the local crystal defects in spin-lattice relaxation are discussed.     

Nuclear quadrupole spin-lattice relaxation in Bi4Ge3O12 single crystals doped with atoms of d or f elements. Crystal field effects in compounds exhibiting anomalous magnetic properties

The nuclear quadrupole spin-lattice relaxation was studied in the range 4.2–300 K for single crystals of Bi₄Ge₃O₁₂ doped with minor amounts (the tenth fractions of mol%) of paramagnetic atoms of Cr, Nd, and Gd. Unusual spin dynamic features were recently found for these crystals at room temperature: a dramatic (up to 8-fold) increase in the effective nuclear quadrupole spin-spin relaxation time T ₂* occurred upon doping the pure Bi₄Ge₃O₁₂ sample. Unlike T ₂*, the effective spin-lattice relaxation time T ₁* at room temperature differs insignificantly for both doped and pure samples. But at lower temperatures, the samples exhibit considerably different behavior of the spin-lattice relaxation with temperature, which is caused by different contributions to the relaxation process of the dopant paramagnetic atoms. The distinctive maximum in the temperature dependence of the spin-lattice relaxation time for the Nd-doped crystal is shown to result from the crystal electric field effects.     

Spin gap, phase separation and d-wave pairing as revealed by electron spin-lattice relaxation in 123 and 124 YBaCuO systems doped with Gd3+

With an original modulation technique, the Gd³⁺ electron spin-lattice relaxation has been investigated in normal and superconducting states of YBa₂Cu₃O_6+x (123) and YBa₂Cu₄O₈ (124) compounds doped with 1% Gd. In the 123 sample withx = 0.9T _c = 90 K), theT ₁ behavior within 50 <T< 200 K reveals the [1 ? tanh²(Δ/2kT)]/T dependence typical of a spin gap opening with Δ ≈ 240 K. Below 50 K, the exponential slowing down ofT ₁ is limited by the Korringa-like behaviorT ₁ T = const); the same Korringa-like law is found in the 123 sample withx = 0.59 (T _c = 56 K) within the total 4.2–200 K temperature range. This is interpreted in terms of microscopic separation of the normal and superconducting phases allowing for the electron spin cross-relaxation between them. In the 124 sample (T _c = 82 K), the Gd³⁺ relaxation rate below 60 K is found to obey a power lawT _n with an exponentn ≈ 3. Such a behavior (previously reported for nuclear spin relaxation) is indicative of the d-wave superconducting pairing. Additional paramagnetic centers characterized by relatively slow spin-lattice relaxation are found in both 123 and 124 systems. A well-pronounced change in theT ₁ temperature dependence atTT* ≈ 180–200 K is observed for these slowly relaxing centers as well as for the conventional, fast-relaxing Gd³⁺ ions, suggesting microscopic phase separation and a change in the relaxation mechanism due to electronic crossover related with the opening of the spin gap. This hypothesis is supported by some “180 K anomalies” previously reported by other authors.     

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.     

La NMR and As NQR study of the As-based filled skutterudite LaOs4As12

We report experimental results of nuclear magnetic resonance (NMR) at the La site and nuclear quadrupole resonance (NQR) at the As site in the normal state of the superconducting compound LaOs₄As₁₂. Measurements have been performed on powder sample obtained from high quality single crystals. The temperature dependences of the nuclear spin-lattice relaxation rates, 1/T₁, of ⁷⁵As and ¹³⁹La nuclei were measured. No scaling between them was found indicating a local character of relaxation processes. The relaxation of ⁷⁵As nuclei can consistently be understood in terms of antiferromagnetic spin fluctuations, as deduced from the T-dependence of (1/T₁T)=C/(T−θ)^1/2.     

Spin-lattice relaxation in the rotating frame and extreme slowing-down at the antiferroelectric transition in copper formate tetrahydrate

The effect on the temperature behavior of the spin-lattice relaxation rates in laboratory and rotating frames in presence of extreme slowing-down of the critical fluctuations in an Ising-type system is discussed. Proton spin-lattice relaxation measurements of T₁ and T_1? in water-deuterated copper formate tetrahydrate are presented. The data shown that the anomalous behavior of the proton T_1? in the neighbourhood of the antiferroelectric phase transition recently observed by Zumer and Pir? in the ordinary crystal cannot be ascribed to the critical slowing-down of the water molecules. A possible interpretation on the basis of a mechanism of creation and annihilation of paramagnetic excitons is discussed.     

Evaluation of muscle degeneration in inherited muscular dystrophy by nuclear magnetic resonance techniques

Nuclear magnetic resonance (NMR) techniques were applied to study the muscular dystrophy in chicks. The water proton spin-lattice relaxation times (T₁) of fast, slow, and mixed muscles and plasma were measured. The T₁ values of dystrophic pectoralis major and posterior latissimus dorsi (PLD) were significantly higher than those of the normal pectoralis and PLD muscles. The present results establish a direct relationship between the differences in T₁ values and the severity of muscle degeneration. Consistent with this conclusion, it was also found that the T₁ values of muscles unaffected in muscular dystrophy, namely, the gastrocnemius, and anterior latissimus dorsi (ALD), were not different between the normal and dystrophic chicks. Although the affected muscles of dystrophic chicks contained higher percent water and fat than those of normal chicks, the results show that the higher T₁ values is dystrophic muscles were not solely due to variations in their water content. The increase in the T₁ values is principally a result of altered interaction between cellular water and macromolecules in the diseased muscles. These data also point out the potential use of NMR imaging in evaluating muscle degeneration.     

Critical anomaly in the electron spin-lattice relaxation at the ferroelectric phase transition of X-irradiated KDA

The spin-lattice relaxation of X-irradiated ferroelectric KDA has been investigated by means of the electron spin-echo method in the range between 2 and 200 K. In the vicinity of the phase transition point an anomalous increase of T₁ has been observed. This effect could not be detected for KDA-KDP mixed crystals with a high concentration of KDP. The anomaly of the spin-lattice relaxation at the phase transition is explained by the increased damping of the “hard” optical mode which governs the relaxation behaviour at this temperature region.     

Phonon-Engpaß und sein Einfluß auf die paramagnetische Relaxation

The coupled spin-lattice and lattice-bath differential equations are solved numerically for the special case of terbium ethyl sulfate. The relaxation decay shows non-exponential behaviour if the lifetime τ of the phonons in direct contact with the spin-system is equal or greater thanT ₁/b.T ₁ is the spin-lattice relaxation time andb the ratio of the specific heats of the spin-system and the phonons in contact with the spin-system. The effective (measured) relaxation timeT _eff depends on the initial disturbance of the spin-system. In a second paper measurements are published which show these predicted effects. In these experiments there has been found a severe phonon bottleneck in the terbium ethyl sulfate.     

Temperature dependence of the spin-lattice relaxation time for quadrupole nuclei under conditions of NMR line saturation

The contributions of different mechanisms of nuclear spin-lattice relaxation are experimentally separated for ⁶⁹Ga and ⁷¹Ga nuclei in GaAs crystals (nominally pure and doped with copper and chromium), ²³Na nuclei in a nominally pure NaCl crystal, and ²⁷Al nuclei in nominally pure and lightly chromium-doped Al₂O₃ crystals in the temperature range 80–300 K. The contribution of impurities to spin-lattice relaxation is separated under the condition of additional stationary saturation of the nuclear magnetic resonance (NMR) line in magnetic and electric resonance fields. It is demonstrated that, upon suppression of the impurity mechanism of spin-lattice relaxation, the temperature dependence of the spin-lattice relaxation time T₁ for GaAs and NaCl crystals is described within the model of two-phonon Raman processes in the Debye approximation, whereas the temperature dependence of T₁ for corundum crystals deviates from the theoretical curve for relaxation due to the spin-phonon interaction.     

Isotope ratio of Cl NQR spin-lattice relaxation times in 1D hydrogen-bonding system of tetramethylpyrazine-chloranilic acid at high temperatures

The temperature dependences of spin-lattice relaxation time T ₁ of ³⁵Cl and ³⁷Cl NQR were studied for the co-crystal of tetramethylpyrazine (TMP) with chloranilic acid (H₂ca), TMP-H₂ca, in which one-dimensional hydrogen bonding is formed by alternate arrangement of TMP and H₂ca. The isotope ratio ³⁷Cl T ₁ / ³⁵Cl T ₁ was determined to be 1.0 ± 0.1 above ca. 290 K where a steep decrease of spin-lattice relaxation time T ₁ with increasing temperature was observed. In this temperature range it is suggested that the relaxation is originated from the slow fluctuation of electric field gradient (EFG). Beside EFG fluctuation due to the external-charge-density fluctuation, the small angle reorientation of the quantization axis triggered by a proton transfer motion between N...H-O and N-H...O hydrogen bonding states is proposed.     

The hardening of Portland cement observed by1H spin-lattice relaxation and single-point imaging

The nature of hydration in ordinary Portland cement samples from different Polish factories was investigated by the proton spin-lattice relaxation timeT ₁ and single-point imaging (SPI). The time dependence of the spin-lattice relaxation timeT ₁ shows the usual behavior:T ₁ is constant at the beginning of hydration (the dormant period), then, during the setting process, decreases to the constant value in the hardening period of hydration. However, there are some anomalies inT ₁ connected with the different amount of the mineral components in the cement sample. The unusual behavior of the stretched parameterα, after about 20 h of hydration, is observed and connected with the microcracking of the cement matrix. The 1-D and 2-D SPI images of the cement paste taken at various times of hydration show the distribution of the water throughout the sample and clearly demonstrate the usefulness of SPI in the study of the internal structure of the porous system.