NMR studies of two unusual f-electron metals

We present the results of nuclear magnetic resonance (NMR) studies down to very low temperatures for two U compounds, UCu_3.5Pd_1.5 and U_0.8Y_0.2Pd₃, where the conduction electrons experience strong interactions and for which the temperature dependences of the thermal and transport properties do not obey the expectations of a simple Fermi-liquid model. Also the temperature and field dependences of the nuclear magnetization recovery of UCu_3.5Pd_1.5 in Cu nuclear quadrupole resonance show unusual features that cannot be reconciled with common expectations for a simple metal, but they are well accounted for by the Kondo disorder model. For U_0.8Y_0.2Pd₃, our Y NMR results indicate a distribution of internal static magnetic fields at the Y sites and a small temperature-dependent enhancement of the spin-lattice relaxation rateT ₁ ^? with respect to YPd₃. The NMR spectra are consistent with the presence of very small frozen U moments, but the temperature dependence of the spin-lattice relaxation rate indicates a more complicated situation.     

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.     

7Li NMR study of the mobility of lithium ions in one-dimensional channels of Nb3Se4

The temperature dependence of the spin-lattice relaxation time T ₁ and the ⁷Li NMR spectra of the Li_0.7Nb₃Se₄ intercalation compound with one-dimensional channel structure have been studied. It is found that the temperature dependence of T ₁ exhibits two relaxation minima, and the quadrupole splitting in the Li NMR spectra shows an anomalous temperature behavior. The inference is drawn that the observed effects are associated with the high-rate diffusive motion of lithium ions along one-dimensional channels and the interchannel transitions.     

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.     

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.     

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.     

Frequency dependence of electron spin-lattice relaxation rate at 5–450 MHz in pristine trans-polyacetylene --- new evidence of one dimensional diffusive motion of electron spin (neutral soliton) ---

Electron spin-lattice relaxation rate T_l^?1 has been measured at low frequencies 5–450 MHz in pristine trans-polyacetylene. Frequency dependence of T_l^?1 gave dimensionality of diffusive motion of electron spins (neutral soliton). Relaxation mechanism was identified as dipolar and hyperfine origin based on an electron spin concentration dependence of T_l^?1.     

Study on vacancy motion in Y2O3-doped CeO2 by 17O NMR technique

The ¹⁷O NMR measurement was made to elucidate the microscopic nature of vacancy motion in Y₂O₃-doped CeO₂. Spin-lattice relaxation rate, T^?1₁, spin-spin relaxation rate, T^?1₂, and resonance intensity were measured at v₀ = 8.13 MHz as a function of temperature [385 < T (K) < 1110] and composition [$\text{0.06 <}\text{Y}{}_2\text{O}{}_3\text{(}\text{m}\text{o}\text{) < 6}$]. The static electric field gradient associated with lattice defects resulted in the composition dependences of the line width and the intensity. In low dopant concentrations, doubly peaked temperature dependence of T^?1₁ was found, while a single and asymmetric peak was observed in high concentrations. T^?1₁ of 4.0 and 6.0 $\text{m}\text{o}$ doped samples were analyzed using a barrier height distribution model for the oxygen vacancy jump. The mean value of the activation energy was found to increase with the Y₂O₃ concentration.     

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.     

Effect of the magnetic field on the 3d ordering and on the spin correlations of the linear antiferromagnet TMMC

The effect of an external magnetic field in the range 6–47 kOe on the low temperature proton spin-lattice relaxation rate in TMMC has been investigated. A peak in T₁^?1 at the 3d ordering temperature has been detected. Values of T_N for fields up to 47 kOe have been determined.     

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 nuclear spin relaxation in β-aluminas

²⁷A$\text{l}$ NMR T₁ measurements for Na-, K-, and Na_0.5K_0.5β-alumina in the temperature range ～5–180K are reported. Both Na- and Kβ-alumina exhibit a nearly linear temperature dependence of the spin-lattice relaxation rate T^?1₁ up to ～55K which is attributed to the presence of two-level system (TLS) tunneling modes. A shallow T₁ minimum at ～30K is observed in Na_0.5K_0.5β-alumina. It is suggested that the origin of this minimum is associated with the distribution of TLS parameters, and may be a low-temperature manifestation of the mixed-alkali effect commonly observed in glasses in the higher temperature ionic hopping regime.     

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.     

Nuclear magnetic resonance studies of CePd2In and LaPd2In at low temperatures

We report on In nuclear magnetic resonance (NMR) and nuclear quadrupolar resonance (NQR) measurements on the new heavy-electron compound CePdZIn over a wide temperature range, from 45 mK up to 30 K. CePd₂In undergoes an antiferromagnetic (AF) phase transition at T _N = 1.23 K involving small localised Ce moments of 0.11 μ_B. In zero field, the spin-lattice relaxation rate T ₁ ^?1 (T) shows remarkable changes in its temperature dependence. Above 3 K, T ₁ ^?1 is constant and 850 sec^?1. Between T _N and 2T _N, (T ₁ T)^?1 = 330 (Ksec)^?1, but rapidly decreases below T _N. A Korringatype relaxation, characteristic for simple metals at low temperatures, with (T ₂ T)^?1 = 17(Ksec)¹ is resumed below 0.6 K. This value is an order of magnitude larger than (T ₁ T)^?1 for LaPd₂In and therefore is associated with low-energy excitations of the itinerant charge carriers with 4f symmetry. The T ₁ ^?1 data at various non-zero magnetic fields fall on a single curve when plotted as a function of (T/H) if H exceeds 3.5 T. Thus the AF ordering, the 4f moment fluctuations and the Kondo screening are drastically suppressed by the application of fields H of the order of 3.5 T.     

NMR and spin-lattice relaxation rate of89Y,63Cu in radiation disordered YBa2Cu3O6.9

NMR line shifts and spin-lattice relaxation rates of⁸⁹Y and⁶³Cu in YBa₂Cu₃O_6.9 were measured in disordered samples irradiated by fast neutrons with a fluence of: ?=5·10¹⁸ cm^?2 (T _c ^ons =70 K), ?=1.2·10¹⁹ cm^?2 (T _c ^ons =20 K), in order to investigate the evolution of spin susceptibility χ_S under irradiation. According to the data obtained, χ_S decreases markedly as structural disorder accumulates in the samples. The variation of χ_S is related closely to that observed in oxygen-depleted YBa₂Cu₃O_7?δ compounds with nearly the sameT _c value. The data for yttrium display some features that are absent in oxygen-depleted samples. The different temperature dependence of the⁸⁹Y and⁶³Cu Knight shifts and the increase of the⁸⁹Y spin-lattice relaxation rate in irradiated samples are discussed in terms of the electron localization effects arising in the CuO₂ planes due to the radiation-induced structural disorder.     

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.     

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.     

Resonant cross-relaxation between Cr3+ and V3+ in Al2O3

Cross-relaxation, which occurs when a V³⁺ transition is resonant with a monitored Cr³⁺ transition, leads to a marked reduction of the spin-lattice relaxation time of Cr³⁺ in Al₂O₃. Measurements and an analysis of the temperature dependence of this effect give a value of 8.34 ± 0.49 cm^?1 for the zero-field splitting of V³⁺, an ion which is strongly coupled to the lattice.     

Co2+ spin-lattice relaxation narrowing of 19F NMR in KCoF3

The temperature dependence of the ¹⁹F NMR linewidth ΔH in KCoF₃ has been measured over the entire paramagnetic solid state region. The dramatic decrease in the hyperfine-broadened, exchange narrowed ΔH that occurs above 200 K is interpreted as arising from fast Co²⁺ single-ion, spin-lattice relaxation. A model theory of the temperature dependence of ΔH is given which incorporates the interplay of exchange and spin lattice relaxation effects on the decay of the spin autocorrelation function.     

Properties of (Bi1/9Na2/3)(Mn1/3Nb2/3)O3 analysed within dielectric permittivity,conductivity, electric modulus and derivative techniques approach

The (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ ceramics with perovskite structure were sintered. The XRD test proved that the samples are cubic (a?=?3.920?±?0.001?Å). Microstructure and atomic composition were determined with a SEM (JSM-5410) equipped with energy dispersion X-ray analyser (ISIS-300). The fluctuation in the chemical composition was found indicating on local disorder. Broadband dielectric spectroscopy in the range 10^?1–3?·?10⁷?Hz was applied within the range of 100–650?K. The real, ?′(f,?T), and imaginary, ?″(f,?T), parts of complex dielectric permitivity characteristics, both in the temperature and frequency domain, show relaxation processes partially covered by electric conductivity. At high temperatures the electric conductivity exhibits a thermally activated behaviour σ(f,?T)?∝?exp(?E _a/kT) but the variable range hopping (VRH) dependence σ?∝?exp[?(T ₀/T)^1/4] is manifested at low temperatures. The derivatives technique in the frequency (??log??/??log?ω) and temperature (??log??/?T) domain enabled various relaxation processes to be distinguished. The data converted to electric modulus representation, M*(f,?T)?=?1/?*, exhibited clearly resolved relaxation peaks. The relaxation times obtained from the peaks position show a slightly non-Arrhenius temperature behaviour with the activation energy varying in 0.4–0.6?eV range and characteristic time of the electric conductivity relaxation of the order of 10^?12?s. The relaxation times can be fitted at better accuracy with the VRH dependence where T ₀ are of the order of 10⁸?K. It is shown that the low frequency ac-conductivity converges to dc-conductivity and the relation σ(0)?～?ω_m?～?τ_m ^?1 typical for the disordered solids applies. The conduction current relaxation relationship behaves in accord with the VRH system: σ_dc?∝?(T/T ₀)^q (e ²/kT) ω_c, where ω_c?=?ν_ph exp[?(T ₀/T)^1/4] is valid for the locally disordered (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ compound.