Mechanism of nuclear spin-lattice relaxation and its field dependence for ultraslow atomic motion

The contribution of ultraslow self-diffusion of polycrystalline benzene molecules to the spin-lattice relaxation of protons is studied as a function of effective magnetic field H ₂ in a doubly rotating frame (DRF). Proton relaxation time T _1ρρ is measured by direct recording of NMR in a rotating frame (RF). The effective fields have a “magic” orientation corresponding to angles arccos(1/√3) in the RF and π/2 in the DRF so that the secular part of the dipole-dipole interactions of protons is suppressed in two orders of perturbation theory, while the nonsecular part becomes predominant. It is found that the diffusion contribution of benzene molecules to proton relaxation time T _1ρρ is a linear function of the square of field H ₂ and exhibits all peculiarities typical of the model of strong collisions generalized to only fluctuating nonsecular dipole interactions in fields exceeding the local field. This means that the model can also be employed in the given conditions. It is shown that perfect agreement with such a dependence can also be obtained in the model of weak collisions if we take into account the concept of the locally effective quantization field, whose magnitude and direction are controlled by the vector sum of field H ₂, and the nonsecular local field perpendicular to it.     

Longitudinal nuclear spin relaxation in solids in a triply rotating coordinate system: Selective observation of the multispin dipole contribution

The longitudinal nuclear spin relaxation in an effective magnetic field H _e3 acting in a triply rotating coordinate system is recorded. Rotating and doubly rotating coordinate systems are employed for strong suppression of the secular nuclear dipole interactions in the first two orders and for separation of higher-order interactions (four-and five-spin). Experiments on protons in polycrystalline benzene showed that the contribution of such multispin dipole interactions to this relaxation can be observed selectively as a pronounced local minimum in the temperature dependence of the relaxation time. This contribution correponds to ultraslow molecular motions with rates ≃ γH _e3≃2π(10¹−10³) s⁻¹ and can be employed to study such motions in detail, including for purposes of identification of the form of the motion. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 5, 335–340 (10 September 1996)     

Spectrometer for studying NMR and relaxation in the doubly rotating frame

A spectrometer is described that ensures observation of NMR and relaxation in the effective field H_c2 acting in the doubly rotating frame (DRF). Unlike conventional NMR spectrometers, the presented apparatus allows the investigation of nuclear spin dynamics and relaxation under conditions of the specially transformed effective multispin dipole-dipole interaction Hamiltonian not studied up to now. The setup is a modified version of the previously described spectrometer for direct recording of NMR in the effective field H_e1 in the singly rotating frame (RF), all its operating functions being retained. The new version of the apparatus is designed for the study of NMR and, especially, spin relaxation of¹H and¹⁹F nuclei in solids under the magic-angle conditions in both the RF and the DRF. It enables one to obtain NMR spectra and longitudinal and transverse nuclear relaxation kinetics in the DRF field H_e2 directly in their final form. In all operating modes, the apparatus is coherent with respect to the NMR frequency in the laboratory frame. In transient modes, it is also coherent with respect to the NMR frequencies in both the RF and the DRF. In all cases the NMR signals are recorded continuously during a single-scan experiment, as a rule not exceeding 1 s. The sensitivity and resolution capability of the spectrometer are superior to those of the starting one. In particular modes, its sensitivity is comparable with that of conventional NMR spectrometers. The apparatus enables one to investigate in detail slow molecular motions in solids with rates ≅γH_e2 ∽ 10³−10⁵ s⁻¹ and ≅γH_e1 ∽ 10⁵−10⁷ s⁻¹; various motion parameters, including multiparticle correlations as well as a motion mechanism, can be extracted from the experimental data.     

Study of slow molecular motions in α-Crystallin by proton magnetic spin-lattice relaxation in the doubly rotating frame

Proton magnetic spin-lattice relaxation in the effective field H₂ acting in the doubly rotating frame (DRF) was first applied to the study of slow internal protein dynamics in the submillisecond range of correlation times in the solid state. In this method the local dipolar magnetic field is reduced by the magic-angle rotating-frame method so that the resonance frequency of the relaxation experiment may be set below the value of the local field. As a result, unachievable by the standard nuclear magnetic resonance (NMR) relaxation techniques, slow molecular motions become experimentally accessible. The second effective field H₂ is produced by the shallow sine-wave phase modulation of the H₁ pulse. The registration of the DRF spin-lattice relaxation signal takes place directly during the continuous H₁ pulse by means of an additional low-frequency radio-frequency coil oriented along the H₀ field and operating at the rotating-frame NMR frequency of 100 kHz. The measurements of the spin-lattice relaxation time in the DRF within a wide temperature range have been performed in dry and hydrated α-crystallin powders. This is the major protein in the eye lens, which prevents the uncontrolled aggregation of proteins and keeps the lens transparent. The results demonstrate that the protein hydration does not change the amplitude of slow side-chain motions but significantly shortens its correlation time: from about 50 to about 0.5 μs in dry and hydrated samples, respectively. The hydration also decreases the activation energy and restricts the distribution of the correlation times.     

Spin-lattice relaxation and Knight shift on protons in the hydrogen-doped superconducting system H0.2La1.8Sr0.2CuO4

Measurements of the spin-lattice relaxation rate and Knight shift on protons in hydrogen-doped superconducting H_0.2La_1.8Sr_0.2CuO₄ samples are performed in the temperature range 4.2–300 K. An anomalous behavior of the spin-lattice relaxation rate is observed at low temperatures T∼20 K. A model is constructed that explains the appearance of carrier-depleted regions in the bulk of the semiconductor on the basis of the formation of a charged defect (proton). Pis’ma Zh. éksp. Teor. Fiz. 63, No. 7, 533–538 (10 April 1996)     

Field dependence of spin-lattice relaxation of Nd3+ ions in Y3Al5O12 crystals

Our studies involve measuring spin-lattice relaxation times for Nd³⁺ ions in yttrium-aluminum garnets over the temperature range 4–50 K at 9.25 and 36.4 GHz for different orientations of the external magnetic field in relation to the crystallographic axes. The temperature dependence of the relaxation rate is described by T ₁ ⁻¹ =AT ⁿ+b exp(−Δ/kT), where n varies from sample to sample, with n=1 for “perfect” samples (i.e., with the longest relaxation times). Here Δ is approximately 130 cm⁻¹, which is the energy of the excited Kramers doublet of the neodymium ion closest to the ground state, and this makes it possible to interpret the second term in T ₁ ⁻¹ as the contribution of two-stage relaxation proceeding through the intermediate level Δ. A strong field dependence of these processes has been discovered: when the frequency was increased fourfold, the relaxation rate increased by a factor of 10. The effect is a specific manifestation of the degeneracy of the excited level, breaking of the symmetry of the crystalline field due to lattice defects, and the prevalence of deformations of a certain type in the spin-lattice interaction. Zh. éksp. Teor. Fiz. 111, 332–343 (January 1997)     

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.     

N.M.R. relaxation time studies in liquid methyl iodide

The spin-lattice relaxation times of the various nuclei in methyl iodide, methyl iodide-d ₃, and carbon-13 methyl iodide (¹³C, ¹H, ²D) were measured between 210 and 350 K. The separation of the proton-proton intermolecular relaxation was accomplished by a dilution study in methyl iodide-d ₃; the resulting intermolecular contribution agreed well with the existing theories for this mechanism. It was found that the spin-rotation interaction contributed significantly to the intramolecular relaxation of both the protons and the carbon-13. For both nuclei the separation of the spin-rotation interaction from the intramolecular dipole-dipole interaction was accomplished without making any assumptions about the temperature dependence of the spin-rotation relaxation time. The resulting spin-rotation relaxation times for both carbon-13 and protons offer evidence that the large spin-rotation effects are due to the methyl group reorientation.     

1H NMR relaxation investigation of herbicides interacting with photosystem II preparations fromSpinacia oleracea L.

The interaction of three common herbicides, paraquat, acifluorfen and alachlor, with spinach chloroplast photosystem II (PS II) was investigated by measuring¹H nuclear magnetic resonance spin-lattice relaxation rates, transient nuclear Overhauser effect (NOE) and NOE spectroscopy (NOESY) spectra. Binding to PS II was detected by (i) the enhancement of single-selective relaxation rates and (ii) the decrease in the optimal mixing time providing maximal cross-peak intensity in NOESY spectra. Titration of relaxation enhancements was used to calculate the dissociation constants (K _d) from the bound state for paraquat (K _d = 292 ± 71 μM⁻¹) and acifluorfen (K _d = 311 ± 58 μM⁻¹). A similarK _d was apparent for alachlor. Double-selective relaxation rates allowed the isolation of dipolar relaxation terms between selected proton pairs wherefrom dynamic features of the bound state were evaluated. In all cases the motional correlation time of bound herbicide (τ_c = 0.1−0.4 ns at 300 K) was found two orders of magnitude slower than in the free-solution state. In the case of alachlor the E and Z isomers were observed to bind differently to PS II and a change in conformation could be hypothesized.     

Nuclear Spin-Lattice Relaxation of 82BrFe

The field dependence of the nuclear spin-lattice relaxation (SLR) of cold implanted ⁸²Br (T ≤ 25 mK) in α-Fe single crystals was investigated with nuclear magnetic resonance of oriented nuclei (NMR/ON) at low temperatures as experimental technique. The SLR at the lattice sites with the hyperfine fields found by earlier NMR/ON experiments was measured as a function of the applied external magnetic field B _ext parallel to the three principle axes [100], [110] and [111] of the iron single crystal. The data were evaluated with the full relaxation formalism in the single impurity limit and for comparison also with the often employed model of a single exponential function with an effective relaxation time T ₁′. With a phenomenological model the high field values of the relaxation rates r _{∞, [100]′} = 6.6(2) · 10⁻¹⁵ T²sK⁻¹, r _{∞, [110]} = 5.4(2) · 10⁻¹⁵ T²sK⁻¹ and r _{∞, [111]} = 5.2(1) · 10⁻¹⁵ T²sK⁻¹ were obtained.     

On-line Surface Area Measurement of Concentrated Slurries using low field spin-lattice relaxation NMR

A method for the rapid on-line determination of surface area and solids content in flowing concentrated slurries using low field NMR spin-lattice relaxation measurements has been developed and demonstrated. The relationship between flow and spin-lattice relaxation time (T₁) of protons in water at 20 MHz was examined using aqueous copper sulfate solutions. The ability to measure surface area and solids concentration in both stagnant (stopped flow) and flowing systems via NMR was demonstrated using several different concentrated aqueous titania and glass slurries (20 to 80 weight percent) for which the dried powder surface area was previously determined via nitrogen adsorption/BET analysis and the solids content determined gravimetrically. Surface areas were also calculated from particle size analysis and found to vary by up to an order of magnitude from the adsorption and NMR results.     

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.     

Low-frequency lattice dynamics in Ba1−x KxBiO3 oxides according to 39K NMR data

The spin-lattice relaxation times T ₁ in Ba_1−x K_xBiO₃ (x=0.3, 0.4, 0.5) were measured in the normal temperature range (20–300 K).A substantial contribution to the spin-lattice relaxation rate from dynamic local distortions of the crystal lattice near potassium atoms is found. The activation energy of this process increases with decreasing potassium concentration, and the frequency of lattice excitations decreases. The nature of the low-frequency lattice dynamics is discussed. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 5, 344–349 (10 September 1999)     

Nuclear spin-lattice relaxation of192Ir in ferromagnetic amorphous alloy Fe-B studied by nuclear orientation

The nuclear spin-lattice relaxation of¹⁹²Ir in the glassy alloy Ir_3.1Fe_80.5B_16.4 has been studied by low-temperature nuclear orientation technique. The thermal cycling method has been used. No dependence on extermal magnetic field in the range 0.25–1.2 T has been observed. Weger’s mechanism seems to play a crucial role.     

Spin–Spin Interactions and Nuclear Magnetic Relaxation in Magnetic Solids

The influence of the orientational fluctuations of the electronic magnetization, which modulate nuclear spin–spin interactions (Suhl–Nakamura and dipole–dipole), on the spin-lattice relaxation of magnetic nuclei with spin I = 1/2 in the magnetically ordered solids has been investigated. It has been shown that this mechanism of the spin-lattice relaxation is less effective in comparison with the process of spin-lattice relaxation caused by the direct fluctuations of hyperfine fields, which appear when there are the fluctuations of electronic magnetization direction.     

31P and 11B NMR in amorphous NiPB alloys near the paramagnetic-ferromagnetic transition

Knight-shift and nuclear spin-lattice relaxation time measurements have been performed between 4.2°K and room temperature on ¹¹B and ³¹P in amorphous NiPB alloys near the para-ferromagnetic transition. The EFG parameters on ¹¹B were found to be ν_Q=200(±20)kHz and η = 0.35 (±0.10). Knight-shift and Korringa spin-lattice relaxation are mainly due to mechanisms involving p electrons. The effect of Ni magnetic clouds results in a broadening of the linewidth. We observed also the occurence of a Giovannini-Heeger-like contribution to the spin-lattice relaxation rate.     

Comparative studies of the NMR of thulium in Tm123 and Tm124 compounds: Evidence for structural and electronic phase separation

The nuclear magnetic relaxation of ¹⁶⁹Tm in TmBa₂Cu₃O_6+x (x=0.1–1.0, Δ x=0.1) and TmBa₂Cu₄O₈ is studied at temperatures below 5 K. In all the samples, the Tm spin-lattice relaxation proceeds via intrinsic paramagnetic centers (PCs) like Cu²⁺ or copper-oxygen spin-polarized clusters. The experimental data for TmBa₂Cu₃O_6+x support the idea of the structural (chemical) micro-phase separation in oxygen-deficient 123 compounds. Apparently, the samples with x⩾0.4 contain hole-poor nonsuperconducting regions, enriched with PCs, and hole-rich (PC-poor) superconducting regions. The volume fraction f _n of the PC-rich phase reaches a maximum value of 0.85 at x=0.4 and decreases monotonically with increasing x (f _n=0.5, 0.3, and 0.25 at x=0.5, 0.6, and 0.7, respectively). The Tm spin-lattice relaxation in the underdoped TmBa₂Cu₄O₈ compound indicates that this sample, in contrast to oxygen-deficient TmBa₂Cu₃O_6+x , has a homogeneous composition. However, the Tm spin-spin relaxation measurements reveal two sorts of the Tm nuclear spins in Tm124, having different NMR spectra and different relaxation times T ₂. The latter result is evidence of electronic phase separation in CuO₂ phases. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 5, 365–370 (10 September 1996) Published in English in the original Russian journal. Edited by Steve Torstveit.     

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.     

Nuclear spin-lattice relaxation in54Mn-MnCl2.4H2O and lower dimensional magnetic systems

We report on nuclear spin-lattice relaxation studies on⁵⁴Mn-MnCl₂.4H₂O and 2-dimensional⁵⁴Mn-Mn(COOCH₃)₂.4H₂O. In the former crystal, we find that at the lowest temperatures a direct process, normally thought of as forbidden, becomes the mechanism for relaxation. In lower dimensional systems the relaxation might be expected to be relatively fast and indeed in the acetate the relaxation timeT ₁ is ≈1000 s in an applied field of 0.2 T for the Mn2 site and is much shorter at lower fields. In 1-dimensional⁵⁴Mn-(CH₃)₄NMnCl₃(TMMC) a significant γ-ray anisotropy is observed on cooling indicating thatT ₁ is also short in this system. The shortness ofT ₁ in the lower dimensional systems suggests that they may be suitable hosts for on-line experiments.     

Temperature and frequency dependence of the spin-lattice relaxation times of E′1 centers in neutron-irradiated quartz glass

Results are reported for measurements of the spin-lattice relaxation times of E′₁ centers in quartz glass, produced by neutron irradiation, with the measurements made at two frequencies 9.25 and 24.0 GHz over a wide temperature interval 1.5–300 K. The experimental data are interpreted on the basis of interaction mechanisms of the spins with two-level systems with excitation energies ∼6, ∼26, and ∼420 cm⁻¹. A small modification of the existing theory allows us to explain a number of features of the observed temperature and frequency dependence of the relaxation rate. The results are compared with the data available in the literature on spin-lattice relaxation of irradiation centers in crystalline quartz and quartz glass. Fiz. Tverd. Tela (St. Petersburg) 39, 1335–1337 (August 1997)