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.     

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.     

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.     

A study on new phase transitions in Cs2CaCl4·2H2O single crystals by observation of Cs NMR

The ¹³³Cs 1/2→−1/2 spin-lattice relaxation rate, , and the spin-spin relaxation rate, , for a Cs₂CaCl₄·2H₂O single crystal have been measured in function of temperature. The dominant relaxation mechanism of this crystal over the whole temperature range investigated here proceeds via quadrupole interaction. The changes in the ¹³³Cs spin-lattice relaxation rate near 325 K (=T_c1) and 360 K (=T_c2) correspond to phase transitions in the crystal. The change in the spin-lattice relaxation rate at T_c1 is small because the crystal lattice does not change very much during this phase transition. The change in near T_c2 is due to the critical slowing down of the soft mode that typically occurs in structural phase transitions. The temperature dependence of the spin-lattice relaxation rate for this crystal has maximum values at about 240 K, which is attributable to the effect of molecular motion as described by Bloembergen-Purcell-Pound theory. The phase transition temperatures T_c1 and T_c2 obtained from the temperature dependence of the relaxation rate is also clear from data obtained using differential scanning calorimetry. Therefore, we know that previously unreported phase transitions occur at 325 and 360 K.     

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.     

NMR spectral densities and two dimensional diffusion in TiS2(NH3)1.0 and TaS2(NH3)x

NMR measurements of proton spin-lattice relaxation times T₁ and T_1? in the layered intercalation compounds TiS₂(NH₃)_1.0 and TaS₂(NH₃)_x (x = 0.8, 0.9, 1.0) are reported as functions of frequency and temperature (100 K – 300 K). These observations probe the spectral density of magnetic fluctuations due to motions of the intercalated molecules at frequencies accessible to the T₁ (4–90 MHz) and T_1? (1–100 kHz) measurements. Since the average molecular hopping time (τ) can be changed by varying temperature, different regions of the spectral density can be examined. For T > 200 K, both T^?1₁ and T^?1_1? vary logarithmically with frequency, reflecting the two dimensional character of the molecular diffusion. The temperature dependence of T₁ suggests that a more accurate picture of the short time dynamics is required. No dependence of relaxation rate on vacancy concentration is found.     

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.     

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.     

Li- and V-NMR study of LiVS2

⁷Li- and ⁵¹V-NMR have been measured to make clear the electronic state in a two-dimensional triangular lattice LiVS₂. Knight shift of both ⁷Li- and ⁵¹V-NMR is almost independent of temperature below the phase transition temperature T_c of about 310 K from the paramagnetic state to non-magnetic state. The ⁵¹V- spin-lattice relaxation rate 1/T₁ reveals an exponential temperature dependence below T_c, indicating a gap structure of electronic state. These results are consistent with a non-magnetic state with a trimer singlet of V³⁺ spins below T_c.     

Site selection NMR study on electronic state in and near vortex core of YBa2Cu4O8

We report a site-selective ¹⁷O spin-lattice relaxation rate T₁⁻¹ in the vortex state of YBa₂Cu₄O₈. We found that T₁⁻¹ at the planar sites exhibits an unusual nonmonotonic NMR frequency dependence. Based on T₁⁻¹ in the vortex core region, we establish strong evidence that the local density of states within the vortex core is strongly reduced.     

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.     

The roles of “ammonium” and “hydrogen-bond” protons in single crystals of the superionic conductor NH4HSeO4 by H NMR relaxation

The variations with temperature of the line-shape, spin-lattice relaxation time, T₁, and spin-spin relaxation time, T₂, of the ¹H nuclei in NH₄HSeO₄ single crystals were investigated, and with these ¹H NMR results we were able to distinguish the crystals’ “ammonium” and “hydrogen-bond” protons. The line width of the signal due to the ammonium protons abruptly narrows near the temperature of the superionic phase transition, T_SI, which indicates that they play an important role in this phase transition. The ¹H T₁ for NH₄⁺ and HSeO₄⁻ in NH₄HSeO₄ do not change significantly near the ferroelectric phase transition of T_C1 (=250 K) and the incommensurate phase transition of T_i (=261 K), whereas they change near the temperature of the superionic phase transition T_SI (=400 K). Our results indicate that the main contribution to the low-temperature phase transition below T_SI is that of the molecular motion of ammonium and hydrogen-bond protons, and the main contribution to the conductivity at high temperatures above T_SI is the breaking of the O-H?O bonds and the formation of new H- bonds in HSeO₄⁻. In addition, we compare these results with those for the NH₄HSO₄ and (NH₄)₃H(SO₄)₂ single crystals, which have similar hydrogen-bonded structure.     

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.     

Mechanism of 3He-mediated nuclear spin-lattice relaxation at surfaces

We measured the nuclear spin-lattice relaxation time T₁, of several surface-bound nuclei, ¹H, ¹⁹F, ¹¹B, ¹³C, ²⁹Si, and ²H, immersed in liquid ³He over the temperature range 0.01 K ⩽ T < 1 K. The Larmor frequencies of these nuclei in a 3.39 T field extended from 22 to 144 MHz. All T₁ values were temperature-independent and ranged from a few seconds to several hours, depending on the particular nucleus and the surface geometry of the sample. The results indicate that the coupled relaxation of surface spins is a phenomenon occurring in all solids immersed in ³He and thus provides a general mechanism for obtaining high nuclear polarization in solids, that the relaxation is controlled by direct dipole-dipole interactions between the surface spins and ³He in the first surface layer, that the ³He motion dynamics do not change appreciably from one surface to another, and that measurements of T₁ may thus be useful for determining the structure of surfaces.     

Nuclear Quadrupole spin-lattice relaxation in Rhombohedral Arsenic

The temperature dependence of the spin-lattice relaxation time T₁ in rhombohedral arsenic has been measured by nuclear quadrupole resonance. The relaxation time is inversely proportional to the temperature and of a magnitude which indicates that the relaxation results from the Fermi contact interaction of the conduction electrons and holes and the arsenic nuclei. The density of electrons and holes at the site of the nucleus, averaged over the Fermi surface is approximately 2.6 × 10²¹ carriers cm^?3.     

Low-temperature spin-lattice relaxation of8Li in the glass Li2O·2SiO2

Nuclear spin-lattice relaxation in Li₂0·2Si0₂ glass below 200 K has been studied using the asymmetric Β-decay radiation of polarized⁸Li (T_1/2=0.Bs) nuclei produced by capture of polarized neutrons. Transients of the⁸Li polarization follow an exp(?√E/T₁) law. The dependence of the spin-lattice relaxation rate ⊥_¯1 ¹ on temperature T and magnetic field B can roughly be described by T_¯1 ¹～T/B. The interpretation is based on the assumption that for⁸Li, contrary to⁷Li in the same glass, spin-diffusion is absent and that each probe nucleus is coupled by quadrupolar interaction to an individual distribution of nearby centres typical of glasses. The fluctuation of these centres causing relaxation may be induced by either a multi-phonon or a thermally activated motional process.     

Nuclear Spin relaxation mediated by Fermi-edge electrons in n-type GaAs

A method based on the optical orientation technique was developed to measure the nuclear-spin lattice relaxation time T ₁ in semiconductors. It was applied to bulk n-type GaAs, where T ₁ was measured after switching off the optical excitation in magnetic fields from 400 to 1200 G at low (< 30 K) temperatures. The spin-lattice relaxation of nuclei in the studied sample with n _D = 9 × 10¹⁶ cm^?3 was found to be determined by hyperfine scattering of itinerant electrons (Korringa mechanism) which predicts invariability of T ₁ with the change in magnetic field and linear dependence of the relaxation rate on temperature. This result extends the experimentally verified applicability of the Korringa relaxation law in degenerate semiconductors, previously studied in strong magnetic fields (several Tesla), to the moderate field range.     

Transitions and Spin Dynamics at Very Low Temperature in the Pyrochlores Yb2Ti2O7 and Gd2Sn2O7

An orientational disorder of the cation in [(PyO)D][AuCl₄] crystal was investigated by the ³⁵Cl NQR and ¹H NMR measurements. A structural phase transition was found at ca. 70 K from the temperature dependence of the NQR frequencies both in [(PyO)D][AuCl₄] and [(PyO)H][AuCl₄]. Temperature dependence of the spin-lattice relaxation time T ₁ of the NQR of [AuCl₄]⁻ could be interpreted by an electric field gradient modulation due to the motion of the cation. Characteristics of T ₁ of ³⁵Cl NQR as well as that of ¹H NMR suggest a dynamic orientational disorder of the cation.     

Cs nuclear magnetic resonance study in CsZnCl3 single crystals of perovskite ABX3 type

CsZnCl₃ single crystals were grown by the slow evaporation method, and the spin-lattice relaxation rates and resonance lines of the ¹³³Cs nuclei in the resulting crystals were investigated using FT NMR spectrometry. The temperature dependence of the relaxation rate of the ¹³³Cs nuclei in the CsZnCl₃ crystals was found to be continuous near T_C (=366 K), and was not affected by this phase transition. Our results for CsZnCl₃ are compared with those obtained previously for other CsBCl₃ (B=Mn, Cu, and Cd) perovskite crystals. The Cs relaxation time of CsCdCl₃ is longer than that of CsMnCl₃. The differences between the atomic weights of Mn, Cu, Zn, and Cd are responsible for the differences between the spin-lattice relaxation times of these single crystals. The influence of paramagnetic ions is also important in these crystals. The differences between the spin-lattice relaxation times of these crystals could also be due to differences between the electron structures of their metal ions, in particular the structures of the d electrons.     

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.