Spin diffusion of dipolar energy in NQR

The theory of spin diffusion was extended to the case of nuclear dipolar order in solids containing paramagnetic impurities and nuclei with spin I > 1/2 having nuclear quadrupole moment. We show that spin diffusion process of dipolar order takes place in solids containing paramagnetic impurities. At the start of relaxation process, the direct relaxation regime is realized with non-exponential time dependence. Then the relaxation regime will be changed to diffusion-limited one. Using obtained expressions for the spin lattice relaxation times for these two relaxation regimes, the diffusion coefficient of the dipolar order in nuclear quadrupole resonance can be estimated from experimental data.     

NMR study of holographic Mn-doped yttrium orthoaluminates

The quadrupole coupling constants, asymmetry parameters and spin-lattice relaxation time of²⁷A1 nuclei have been studied in Mn-doped YAlO₃ crystals. The dependence of the relaxation time on temperature and concentration of Mn ions implies a mechanism of relaxation via Mn²⁺ paramagnetic ions taking into account the nuclear spin diffusion partly restricted by the diffusion barrier. A substantial increase of the relaxation times was observed in the photoexposed samples. We ascribe this effect to the appearance of fast-relaxing Mn⁵⁺ ions produced by photoionization of Mn⁴⁺ centers.     

Spin relaxation studies on conducting poly(tetrathiafulvalene)

Magnetic parameters and the relaxation behavior of paramagnetic centers in an iodine-doped poly(tetrathiafulvalene) semiconductor with a d.c. conductivity of 10^?5 S·cm^?1 have been studied using mainly the 2 mm waveband EPR technique in the temperature range of 110–270 K. The EPR line shape analysis confirms the existence of immobile radicals pinne on short polymer chains and mobile polarons with different relaxation parameters in slightly doped poly(tetrathiafulvalene). The temperature dependences of electron spin-lattice and spin-spin relaxation times of paramagnetic centers of both types have been determined independently using the saturation method at the operation frequency ν _e = 140 GHz. An anisotropic slow libration of immobile polarons with an activation energy of 0.02 eV have been registered for the first time using the saturation transfer EPR method. The temperature dependences of intrachain diffusion and interchain hopping rates in poly(tetrathiafulvalene) are determined from theT ₁ andT ₂ EPR data. The interchain spin dynamics is shown to correlate with libration of polarons trapped on polymer chains and is in good agreement with a hopping charge transport mechanism.     

Relaxation of protons by radicals in rotationally immobilized proteins

Proton spin-lattice relaxation by paramagnetic centers may be dramatically enhanced if the paramagnetic center is rotationally immobilized in the magnetic field. The details of the relaxation mechanism are different from those appropriate to solutions of paramagnetic relaxation agents. We report here large enhancements in the proton spin-lattice relaxation rate constants associated with organic radicals when the radical system is rigidly connected with a rotationally immobilized macromolecular matrix such as a dry protein or a cross-linked protein gel. The paramagnetic contribution to the protein-proton population is direct and distributed internally among the protein protons by efficient spin diffusion. In the case of a cross-linked-protein gel, the paramagnetic effects are carried to the water spins indirectly by chemical exchange mechanisms involving water molecule exchange with rare long-lived water molecule binding sites on the immobilized protein and proton exchange. The dramatic increase in the efficiency of spin relaxation by organic radicals compared with metal systems at low magnetic field strengths results because the electron relaxation time of the radical is orders of magnitude larger than that for metal systems. This gain in relaxation efficiency provides completely new opportunities for the design of spin-lattice relaxation based contrast agents in magnetic imaging and also provides new ways to examine intramolecular protein dynamics.     

Anomalous surface diffusion of water compared to aprotic liquids in nanopores

1H nuclear magnetic relaxation dispersion experiments show remarkable differences between water and acetone in contact with microporous glass surfaces containing trace paramagnetic impurities. Analyzed with surface relaxation theory on a model porous system, the data obtained for water show that proton surface diffusion limited by chemical exchange with the bulk phase permits long-range effectively one-dimensional exploration along the pores. This magnetic-field dependence coupled with the anomalous temperature dependence of the relaxation rates permits a direct interpretation in terms of the proton translational diffusion coefficient at the surface of the pores. A universal rescaling applied to these data collected for different pore sizes and on a large variety of frequencies and temperatures, supports this interpretation. The analysis demonstrates that acetone diffuses more slowly, which increases the apparent confinement and results in a two-dimensional model for the molecular dynamics close to surface relaxation sinks. Surface-enhanced water proton diffusion, however, permits the proton to explore a greater spatial extent of the pore, which results in an apparent one-dimensional model for the diffusive motions of the water that dominate nuclear spin relaxation.     

Pulsed EPR hole-burning experiment on dangling bond centers in a-Si:H aerosol particles formed by thermal decomposition of silane

Si dangling bond centers in aerosol particles of amorphous hydrogenated silicon formed by thermal decomposition of SiH₄ in Ar were studied by pulsed electron paramagnetic resonance. The hole-burning and inversion-recovery experiments demonstrate that large-scale rapid spectral diffusion takes place in the samples with high spin concentration. Correlation times τ_c of the spectral diffusion and spin-lattice relaxation timesT ₁ were obtained in the temperature range between 77 and 290 K. Above 130 K, τ_c andT ₁ are proportional one to the other. The unusual feature of this spectral diffusion is that the shape of the central part of the spectral hole does not change when the delay time increases. The other paramagnetic centers previously investigated showed a remarkable change of the hole shape which was induced by modulation of dipolar interaction due to spin flips. It is suggested that the observed anomaly in the Si dangling bond centers arises due to cooperative spin flips.     

未掺杂反式聚乙炔(CH)x中核自旋晶格弛豫-孤子-维扩散模型

Nechtschein等人报道并分析了反式聚乙炔中质子自旋晶格弛豫时间对拉摩频率ω和温度T的依赖关系。观察到了质子自旋晶格弛豫速率T₁^-1和ω^-1/2的正比关系。但是在高频段,T₁^-1∝ω^-1/2关系发生偏离,且温度越低,发生偏离的频率也越低。 本文用另一种方法对这些实验结果作了分析。首先,论证了孤子一维扩散模型的合理性。排除了质子弛豫速率∝ω^-1/2的另一种解释,即仅仅是核自旋向着静止的顺磁中心扩散。孤子能处在运动状态或静止状态。当温度降低时,发生两个效应,即越来越少的孤子处于运动状态,且运动孤子的扩散系数减小。只有扩散的孤子对所观察到的质子弛豫有贡献,而固定孤子的贡献可以忽略。其次,描述了运动孤子的一维随机行走模型,计算了它的相关函数和谱密度函数。质子自旋晶格弛豫速率是: 其中C是运动孤子的浓度,τ是运动孤子沿链跳跃时,渡越相邻位置的跳跃时间,ω是质子的拉摩频率。 这个公式揭示了质子弛豫速率的频率和温度依赖关系的主要特征。它和Nechtschein的测量结果拟合得很好。从拟合中可以得到各个温度下运动孤子的跳跃时间和相对浓度。     

Rotating frame proton spin relaxation in viscous glycerol

The observation of a rotating frame Larmor frequency dependence in the proton spin relaxation of glycerol lends support to a recent study of proton spin relaxation in this substance. Comparison of the data to recent theories describing spin relaxation by translational diffusion strongly suggest that this is the dominant relaxation process in glycerol near room temperature. In addition, the measurement of the self-diffusion coefficient of glycerol, at a temperature lower than has been previously reported, indicates that this rotating frame technique may be useful in the study of diffusion in viscous media.     

Behavior of positive muons in highT c superconductors La2−x Sr x CuO4

An unambiguous determination of the ⁺ location in the highT _c LaSrCuO superconductor is made through zero-field spin relaxation in the paramagnetic phase and its crystal axis dependence by using single crystalline samples. The temperature dependence of the relaxation rates has a maximum between 80 and 150 K, indicating the existence of the onset of quantum diffusion at low temperature.     

Oxygen effect on spin relaxation of the surface paramagnetic centers in carbon chars

The original technique with the use of longitudinal electron paramagnetic resonance detection was applied to measure longitudinal and transversal electron relaxation times (T ₁ andT ₂) in specially prepared carbon chars containing paramagnetic centers (PCs) on the surface. The results not only confirmed the conclusions of our previous studies but enabled us to determine the exchange integral and clarify the mechanism of interaction between the PCs and adsorbed molecular oxygen O₂. A spin relaxation mechanism was also suggested which takes into account both the exchange and dipolar interactions in the systems combining PC and O₂. The value of the exchange integral between PCs as well as its functional dependence on the oxygen content were estimated.     

Magnetoplastic effect and spin-lattice relaxation in a dislocation-paramagnetic-center system

A magnetic induction threshold B _c above which the magnetoplastic effect — depinning of dislocations from paramagnetic pinning centers — can be observed in samples placed in a magnetic field is predicted and observed in Al, NaCl, and LiF crystals. The existence of a threshold is associated with the fact that for B<B _c the spin-lattice relaxation time τ_sl in a dislocation-paramagnetic-center system is less than the time required for spin evolution in a magnetic field resulting in the removal of the spin forbiddenness of an electronic transition that “switches off” the dislocation-pinning-center interaction. It is shown that the threshold field B _c is sensitive to temperature and x-ray irradiation of the samples. A new method for measuring the spin-lattice relaxation time in paramagnetic centers on dislocations is proposed on the basis of the data obtained. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 8, 628–633 (25 April 1996)     

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.     

Spin diffusion and nuclear spin-lattice relaxation in irradiated solids: a multiple-pulse NQR study

We present a detailed theoretical and experimental NQR multiple-pulse spin-locking study of spin-lattice relaxation and spin diffusion processes in the presence of paramagnetic impurities in solids. The relaxation function of the nuclear spin system at the beginning of the relaxation process is given by exp , where T_1ρ is spin-lattice relaxation time in rotating frame and =d/6, d is the sample dimensionality. Then the relaxation proceeds asymptotically to an exponential function of time, which was attributed to the spin-diffusion regime. Using the experimental data obtained from the analysis of those two relaxation regimes in γ-irradiated powdered NaClO₃, spin diffusion coefficient has been determined and the radius of the diffusion barrier has been estimated.     

Effects of paramagnetic cations on the nonexponential spin-lattice relaxation of rare spin nuclei in solids

Nonexponential spin-lattice relaxation is often observed for rare spin nuclei in the solid state. Deviation from single-component decay may be amplified by the coupling of rare spin nuclei to paramagnetic centers. Nonexponential spin-lattice relaxation was observed in derivatized silica gels resins. This phenomenon was localized and enhanced when paramagnetic transition metal cations were bound to surface functional groups. A stretched exponential analysis method was determined to be robust in fitting nonexponential relaxation curves for silica gels both with and without bound paramagnetic ions. Spin-lattice relaxation rates (T₁⁻¹) for functional group nuclei increased as a function of percent surface coverage with metal ion. The magnitude of the relaxation rate increase was dependent upon internuclear distances from the paramagnetic center. At low surface coverages, a semi-random distribution of paramagnetic centers increased the degree of stretching of spin-lattice relaxation decays, as measured by decreases in the calculated stretching parameter β. At higher surface coverages, calculated β values reached a limiting value, indicating that while the spin-diffusion mechanism in metal-ex-changed silica gels is restricted, it is not completely diminished.     

Paramagnetic relaxation in sandstones: distinguishing T1 and T2 dependence on surface relaxation, internal gradients and dependence on echo spacing

This work provides a generalized theory of proton relaxation in inhomogeneous magnetic fields. Three asymptotic regimes of relaxation are identified depending on the shortest characteristic time scale. Numerical simulations illustrate that the relaxation characteristics in the regimes such as the T(1)/T(2) ratio and echo spacing dependence are determined by the time scales. The theoretical interpretation is validated for fluid relaxation in porous media in which field inhomogeneity is induced due to susceptibility contrast of fluids and paramagnetic sites on pore surfaces. From a set of measurements on model porous media, we conclude that when the sites are small enough, no dependence on echo spacing is observed with conventional low-field NMR spectrometers. Echo spacing dependence is observed when the paramagnetic materials become large enough or form a 'shell' around each grain such that the length scale of the region of induced magnetic gradients is large compared to the diffusion length during the time of the echo spacing. The theory can aid in interpretation of diffusion measurements in porous media as well as imaging experiments in presence of contrast agents used in MRI.     

Exchange and dipolar spin-spin interaction and rotational diffusion in saturation transfer EPR spectroscopy

Saturation transfer EPR spectroscopy (STEPR) provides a means for investigating weak spin-spin interaction between spin-labelled molecules because the spectral intensity is proportional to the effective spin-lattice relaxation time,T ₁ ^eff. Rate equations for the spin population defferences yield equivalent results for the dependence ofT ₁ ^eff on the physical (or chemical) and Heisenberg spin exchange rates and show thatT ₁ ^eff depends on the extent of redistribution of saturation throughout the anisotropic spin label powder lineshape. This approach yields a particularly simple formulation for the dependence of the STEPR lineshape on slow rotational diffusion. The effects of spin exchange are readily distinguished from those of slow rotational diffusion because of the insensitivity of the STEPR lineshape in the former case. The characteristic dependence of the STEPR spectral intensity on spin concentration allows determination of the exchange rate and can be used for studying slow translational diffusion, e.g. of spin-labelled proteins. Dipolar relaxation induced by paramagnetic ions gives a linear dependence of the reciprocal spin label STEPR intensity on metal ion concentration. STEPR measurements with spin-labelled lipid molecules in gel phase membranes in the presence of Ni²⁺ ions yield reliable distance information and provide calibrations for use with other systems.     

A pulsed EPR method to determine distances between paramagnetic centers with strong spectral anisotropy and radicals: The dead-time free RIDME sequence

Methods to determine distances between paramagnetic metal centers and radicals are scarce. This is unfortunate because paramagnetic metal centers are frequent in biological systems and so far have not been employed much as distance markers. Successful pulse sequences that directly target the dipolar interactions cannot be applied to paramagnetic metal centers with fast relaxation rates and large g-anisotropy, if no echos can be detected and the excitation bandwidth is not sufficient to cover a sufficiently large part of the spectrum. The RIDME method Kulik et al. (2002) [20] circumvents this problem by making use of the T₁-induced spin-flip of the transition-metal ion. Designed to measure distance between such a fast relaxing metal center and a radical, it suffers from a dead time problem. We show that this is severe because the anisotropy of the metal center broadens the dipolar curves, which therefore, only can be analyzed if the full curve is known. Here, we introduce five-pulse RIDME (5p-RIDME) that is intrinsically dead-time free. Proper functioning of the sequence is demonstrated on a nitroxide biradical. The distance between a low-spin Fe(III) center and a spin label in spin-labeled cytochrome f shows the complete dipolar trace of a transition-metal ion center and a spin label, yielding the distance expected from the structure.     

Kernrelaxations-Untersuchung der Selbstdiffusion in festem Kupfer

We report on measurements of the⁶³Cu nuclear spin relaxation time in the rotating frame,T _1ρ, in solid copper as a function of temperature and Larmor frequency, from which the temperature dependence of the self-diffusion coefficient was evaluated using Torrey's theory. Within the relatively small temperature range (572 °C ≦ ? ≦ 838 °C) in which diffusion relaxation dominates, the temperature dependence of the diffusion coefficient is compatible with a simple Arrhenius law. However, in an evaluation including recent tracer results in an essentially larger temperature range (353 °C≦?≦1079 °C) clear deviations from this standard interpretation were found, as implied by Seeger's divacancy formalism. From those deviations we have calculated a more reliable set of diffusion parameters than comparable data in the literature.     

Surface nuclear magnetic relaxation and dynamics of water and oil in granular packings and rocks

Low field proton nuclear spin-relaxation at variable magnetic field strength and temperature provides surface dynamical parameters such as surface diffusion coefficients, activation energies, time of residence and coefficient of surface affinity. These parameters were extracted from measurements on grain packs and natural oil-bearing rocks. On grain packs, we show first that changing the amount of surface paramagnetic impurities leads to striking different relationships between the pore-size and the relaxation times T1 and T2. These relationships are well supported by fast-diffusion (surface-limited) or slow-diffusion relaxation models. Surface relaxivity parameters rho1 and rho2 are deduced from the pore size dependence in the fast-diffusion regime. Then, we evidence the frequency and temperature dependence of the surface relaxivity rho1 by field cycling NMR relaxation and relevant theoretical models. The typical frequency dependence found allows an experimental separation of the surface and bulk microdynamics in granular packings and petroleum rocks and the determination of the above mentioned surface dynamical parameters. Finally, we present the first field cycling nuclear spin relaxation experiments performed in water/oil saturated petroleum rocks. We believe that these experiments give new information about the surface localization of these two saturating liquids in pores.     

Decay of dipolar order in diamagnetic and paramagnetic proteins and protein gels

Magnetic relaxation in solids may be complicated by the creation and loss of dipolar order at finite rates. In tissues the molecular and spin dynamics may be significantly different because of the relatively high concentration of water. We have applied a modified Jeneer-Broekaert pulse sequence to measure dipolar relaxation rates in both dry and hydrated protein systems that may serve as magnetic models for tissue. In lyophilized and dry serum albumin, the dipolar relaxation time, T(1D) is on the order of 1 ms and is consistent with earlier reports. When hydrated by deuterium oxide, the dipolar relaxation times measured were on the order of tens of microseconds. When paramagnetic centers are included in the protein, the Jeneer-Broekaert echo decay times became the order of the decay time for transverse magnetization, i.e., the order of 10 micros or less. In the hydrated or paramagnetic systems, the dipolar relaxation times are too short to require inclusion in the quantitative analysis of magnetization transfer experiments.