Nuclear spin-lattice relaxation in transition metal alloys and intermetallics

General analytical formulae describing the various contributions to the total spin-lattice relaxation rate in metallic materials (single crystals or powders) are presented. The formulae are obtained in the tight-binding approximation and can be easily used for any point-group symmetry. The cubic (O(h)), hexagonal (D(3h)), and tetragonal (D(2d)) symmetries are considered in detail.     

Molecular oxygen spin-lattice relaxation in solutions measured by proton magnetic relaxation dispersion

Proton spin-lattice relaxation rate constants have been measured as a function of magnetic field strength for water, water-glycerol solution, cyclohexane, methanol, benzene, acetone, acetonitrile, and dimethyl sulfoxide. The magnetic relaxation dispersion is well approximated by a Lorentzian shape. The origin of the relaxation dispersion is identified with the paramagnetic contribution from molecular oxygen. In the small molecule cases studied here, the effective correlation time for the electron-nuclear coupling may include contributions from both translational diffusion and the electron T(1). The electron T(1) for molecular oxygen dissolved in several solvents was found to be approximately 7.5 ps and nearly independent of solvent or viscosity.     

The dipolar and exchange contributions to the spin-lattice relaxation of the imino protons in poly(rA)· poly(rU)

Selective, semiselective, and biselective excitation has been used to study the spin-lattice relaxation of the hydrogen-bonded imino protons in the sonicated, double-stranded RNA polymer poly(rA)· poly(rU). The spin-lattice relaxation of the imino protons has contributions from both dipolar interactions and exchange with the solvent, and the relative contribution of each to the observed rate depends on temperature. When exchange is slow compared to the dipolar contribution, the two components can be resolved by measuring the relaxation rate with and without prior inversion of the solvent peak. When exchange is fast, the contributions can be resolved by comparing the initial selective relaxation rate with the rate of saturation transfer when the solvent peak is inverted. This allows the exchange and dipolar contributions to be separated at temperatures well below the duplex melting temperatures and provides an easy way to study the mechanism of proton exchange with the solvent.     

Electron spin relaxation of copper(II) complexes in glassy solution between 10 and 120 K

The temperature dependence, between 10 and 120 K, of electron spin-lattice relaxation at X-band was analyzed for a series of eight pyrrolate-imine complexes and for ten other copper(II) complexes with varying ligands and geometry including copper-containing prion octarepeat domain and S100 type proteins. The geometry of the CuN4 coordination sphere for pyrrolate-imine complexes with R=H, methyl, n-butyl, diphenylmethyl, benzyl, 2-adamantyl, 1-adamantyl, and tert-butyl has been shown to range from planar to pseudo-tetrahedral. The fit to the recovery curves was better for a distribution of values of T1 than for a single time constant. Distributions of relaxation times may be characteristic of Cu(II) in glassy solution. Long-pulse saturation recovery and inversion recovery measurements were performed. The temperature dependence of spin-lattice relaxation rates was analyzed in terms of contributions from the direct process, the Raman process, and local modes. It was necessary to include more than one process to fit the experimental data. There was a small contribution from the direct process at low temperature. The Raman process was the dominant contribution to relaxation between about 20 and 60 K. Debye temperatures were between 80 and 120 K. For samples with similar Debye temperatures the coefficient of the Raman process tended to increase as gz increased, as expected if modulation of spin-orbit coupling is a major factor in relaxation rates. Above about 60 K local modes with energies in the range of 260-360 K (180-250 cm-1) dominated the relaxation. For molecules with similar geometry, relaxation rates were faster for more flexible molecules than for more rigid ones. Relaxation rates for the copper protein samples were similar to rates for small molecules with comparable coordination spheres. At each temperature studied the range of relaxation rates was less than an order of magnitude. The spread was smaller between 20 and 60 K where the Raman process dominates, than at higher temperatures where local modes dominate the relaxation. Spin echo dephasing time constants, Tm, were calculated from two-pulse spin echo decays. Near 10 K Tm was dominated by proton spins in the surroundings. As temperature was increased motion and spin-lattice relaxation made increasing contributions to Tm. Near 100 K spin-lattice relaxation dominated Tm.     

Nuclear spin-lattice relaxation in 3d ferromagnetic metals

The contributions to nuclear spin-lattice relaxation at low, intermediate and high applied magnetic fields in 3d ferromagnetic alloys are discussed. The analysis of nuclear orientation experiments is considered and the various experimental techniques briefly reviewed. Some results for the relaxation rate for cobalt nuclei in iron are compared and some recent high-field data for⁶⁰CoFe are presented showing that an indirect spin-wave process is relatively weak.     

Electron spin relaxation enhancement measurements of interspin distances in human, porcine, and Rhodobacter electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO)

Electron transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO) is a membrane-bound electron transfer protein that links primary flavoprotein dehydrogenases with the main respiratory chain. Human, porcine, and Rhodobacter sphaeroides ETF-QO each contain a single [4Fe-4S](2+,1+) cluster and one equivalent of FAD, which are diamagnetic in the isolated enzyme and become paramagnetic on reduction with the enzymatic electron donor or with dithionite. The anionic flavin semiquinone can be reduced further to diamagnetic hydroquinone. The redox potentials for the three redox couples are so similar that it is not possible to poise the proteins in a state where both the [4Fe-4S](+) cluster and the flavoquinone are fully in the paramagnetic form. Inversion recovery was used to measure the electron spin-lattice relaxation rates for the [4Fe-4S](+) between 8 and 18K and for semiquinone between 25 and 65K. At higher temperatures the spin-lattice relaxation rates for the [4Fe-4S](+) were calculated from the temperature-dependent contributions to the continuous wave linewidths. Although mixtures of the redox states are present, it was possible to analyze the enhancement of the electron spin relaxation of the FAD semiquinone signal due to dipolar interaction with the more rapidly relaxing [4Fe-4S](+) and obtain point-dipole interspin distances of 18.6+/-1A for the three proteins. The point-dipole distances are within experimental uncertainty of the value calculated based on the crystal structure of porcine ETF-QO when spin delocalization is taken into account. The results demonstrate that electron spin relaxation enhancement can be used to measure distances in redox poised proteins even when several redox states are present.     

Electron spin relaxation of copper(II) ions in diamagnetic crystals

The electron spin-lattice and spin-spin phase relaxation measurements of Cu²⁺ ions in various crystals are reviewed and discussed. Examples of the Debye temperature determination from a wide temperature range measurements of the spin-lattice relaxation time T₁ are shown. An influence of the Jahn-Teller dynamics on T₁ is presented. The phase relaxation described by the phase memory time T_M is affected by temperature due to the spin packet width modulation by molecular motions. The T_M is anisotropic in crystals and can be different for different hyperfine lines of an EPR spectrum.     

Magnetization-recovery experiments for static and MAS-NMR of I=3/2 nuclei

Multifrequency pulsed NMR experiments on quadrupole-perturbed I=3/2 spins in single crystals are shown to be useful for measuring spin-lattice relaxation parameters even for a mixture of quadrupolar plus magnetic relaxation mechanisms. Such measurements can then be related to other MAS-NMR experiments on powders. This strategy is demonstrated by studies of (71)Ga and (69)Ga (both I=3/2) spin-lattice relaxation behavior in a single-crystal (film) sample of gallium nitride, GaN, at various orientations of the axially symmetric nuclear quadrupole coupling tensor. Observation of apparent single-exponential relaxation behavior in I=3/2 saturation-recovery experiments can be misleading when individual contributing rate processes are neglected in the interpretation. The quadrupolar mechanism (dominant in this study) has both a single-quantum process (T(1Q1)) and a double-quantum process (T(1Q2)), whose time constants are not necessarily equal. Magnetic relaxation (in this study most likely arising from hyperfine couplings to unpaired delocalized electron spins in the conduction band) also contributes to a single-quantum process (T(1M)). A strategy of multifrequency irradiation with observation of satellite and/or central transitions, incorporating different initial conditions for the level populations, provides a means of obtaining these three relaxation time constants from single-crystal (71)Ga data alone. The (69)Ga results provide a further check of internal consistency, since magnetic and quadrupolar contributions to its relaxation scale in opposite directions compared to (71)Ga. For both perpendicular and parallel quadrupole coupling tensor symmetry axis orientations small but significant differences between T(1Q1) and T(1Q2) were measured, whereas for a tensor symmetry axis oriented at the magic-angle (54.74 degrees ) the values were essentially equal. Magic-angle spinning introduces a number of complications into the measurement and interpretation of the spin-lattice relaxation. Comparison of (71)Ga and (69)Ga MAS-NMR saturation-recovery curves with both central and satellite transitions completely saturated by a train of 90 degrees pulses incommensurate with the rotor period provides the simplest means of assessing the contribution from magnetic relaxation, and yields results for the quadrupolar mechanism contribution that are consistent with those obtained from the film sample.     

spin-lattice relaxation in cobalt-containing aluminophosphate molecular sieves

Phosphorus spin-lattice relaxation was studied in aluminophosphate molecular sieves containing various concentrations of either framework or non-framework cobalt. The behaviour of nuclear magnetisation in the presence of these paramagnetic centres was described successfully in the limit of no spin-diffusion. The diffusionless regime was strongly indicated with non-exponential magnetisation recovery and was therefore easy to recognise. According to the model, spin-lattice relaxation rates depend on the square of cobalt concentration. Measured relaxation rates agreed well with calculations if effective cobalt concentration was considered rather than the average one. The latter was obtained by bulk elemental analysis, while the former was extracted from cobalt concentration depth-profiles measured with Auger electron spectroscopy. These measurements indicated that in impregnated samples containing non-framework cobalt there could be much more cobalt near the crystal surface than within the crystal. Because high cobalt concentration can lead to an invisible phosphorus, only nuclei deep within the crystal contribute to the NMR signal. In such a case, the effective concentration is simply the concentration of cobalt far from the crystal surface. In our case, two impregnated samples with different bulk cobalt concentrations exhibited equal relaxation rates. Previously, such a case was misinterpreted as a case, in which nuclear spin-lattice relaxation was independent of cobalt concentration. AES measurements, however, revealed, that although average concentrations of the two samples were different by a factor of two, their effective concentrations were equal and thus in complete agreement with observed relaxation rates.     

spin-lattice relaxation in cobalt-containing aluminophosphate molecular sieves

Phosphorus spin-lattice relaxation was studied in aluminophosphate molecular sieves containing various concentrations of either framework or non-framework cobalt. The behaviour of nuclear magnetisation in the presence of these paramagnetic centres was described successfully in the limit of no spin-diffusion. The diffusionless regime was strongly indicated with non-exponential magnetisation recovery and was therefore easy to recognise. According to the model, spin-lattice relaxation rates depend on the square of cobalt concentration. Measured relaxation rates agreed well with calculations if effective cobalt concentration was considered rather than the average one. The latter was obtained by bulk elemental analysis, while the former was extracted from cobalt concentration depth-profiles measured with Auger electron spectroscopy. These measurements indicated that in impregnated samples containing non-framework cobalt there could be much more cobalt near the crystal surface than within the crystal. Because high cobalt concentration can lead to an invisible phosphorus, only nuclei deep within the crystal contribute to the NMR signal. In such a case, the effective concentration is simply the concentration of cobalt far from the crystal surface. In our case, two impregnated samples with different bulk cobalt concentrations exhibited equal relaxation rates. Previously, such a case was misinterpreted as a case, in which nuclear spin-lattice relaxation was independent of cobalt concentration. AES measurements, however, revealed, that although average concentrations of the two samples were different by a factor of two, their effective concentrations were equal and thus in complete agreement with observed relaxation rates.     

有机磷化合物的NMR研究——Ⅱ0,0-二烷基膦酸酯的1H、13C和31PNMR谱

本文报道了21个0,0一二烷基膦酸酯类化合物的¹H、¹³C和³¹P NMR参数。研究和讨论了不等价的二烷基¹H、¹³C化学位移和磷碳偶合常数与立体化学的关系。测定了(CH₃CH₂O)₂P(O)CH(CH₂NO₂)(p-OCH₃C₆H₄)的¹³C自旋一晶格弛豫时间T₁,二乙基¹³C T₁间的差别,说明在类似化合物中,含有化学位移各向异性对弛豫的贡献。     

Electron spin relaxation via vibronic level of rhodium(II) hexacyanide complex in KCl crystal

Electron spin-lattice relaxation rates for the low-spin [Rh(CN)(6)](4-) complex in KCl were measured by the inversion recovery and saturation recovery techniques, in the range of 5 to 30 K. Angular variation experiments indicate that electron spin-lattice relaxation times present axial symmetry. The data fit very well to a relaxation process involving localized anharmonic vibration modes, also responsible for the g tensor temperature dependence.     

Proton spin-lattice relaxation in binary liquid mixtures: determination of the mixed translational contributions

Proton spin-lattice relaxation measurements in some binary liquid mixtures suggest a method for determining, with the BPP translational model, the relaxation contributions related to the coupling of protons belonging to molecules of different types. These mixed translational contributions can be evaluated when the experimental values of the apparent relaxation time and those corresponding to ideal behaviour are not very different. When the translational relaxation times corresponding to the mixed contributions are shorter than the translational relaxation times related to molecules of the same type, a decrease in the reciprocal mobility occurs which involves interaction phenomena such as molecular associations and structure-breaking processes. The opposite case refers to the existence of rather stable structures.     

Magnetic resonance and relaxation in structurally incommensurate systems

The present state of theoretical and experimental magnetic resonance investigations of structurally incommensurate systems is reviewed. The magnetic resonance lineshapes and the temperature and frequency dependences of the spin-lattice relaxation rates are evaluated in the plane wave and multisoliton limits. In contrast to translationally periodic systems, the spin-lattice relaxation rate is shown to vary over the incommensurate resonance line and is determined by phason and amplitudon fluctuations. The variation of the relaxation rate over the incommensurate line allows for a separate determination of the amplitudon and phason contributions as well as a discrimination between direct and Raman processes. The results further demonstrate that the soliton width is large as compared to the intersoliton spacing over most of the incommensurate phase.     

Rapid computer simulation of E.S.R. spectra

A fast computer algorithm is presented which permits simulation of the effects of rotational diffusion, electron and nuclear relaxation, microwave power, and modulation frequency upon saturation transfer (passage) E.S.R. spectra. Comparison of theoretical and experimental spectra for nitroxide spin-labelled biomolecules suggests that while the dependence of electron spin-lattice relaxation time upon rotational correlation time is weak, the variation of the ratio of the electron to nuclear spin-lattice relaxation times is significant and consideration of strong nuclear relaxation is necessary for the simulation of spectra characterized by correlation times near the reciprocal of the nitrogen nuclear resonance frequency.     

<Superscript>23</Superscript>Na spin-lattice relaxation in powder Rochelle salt

The temperature dependence of ²³Na spin-lattice relaxation in the polycrystalline Rochelle salt was studied by NMR within the range from 235 to 320 K covering both Curie points. The spin-relaxation time t ₁ versus temperature curve showed noticeable dips near the phase transitions against the background of the regular decrease in the relaxation time upon increasing temperature. The dips observed were ascribed to critical contributions to sodium spin-lattice relaxation caused by the slowdown of the correlation time for one of two relaxation modes in the Rochelle salt. The ²³Na NMR parameters were also measured for the melted Rochelle salt. This article was submitted by the authors in English.     

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.     

A Mössbauer study of potassium ferric alum

The first temperature-dependent Mössbauer spectra from polycrystalline samples of KFe alum are presented. The FWHM varies considerably with temperature. Application of isotropic relaxation theory suggests that the variation is caused by a change in electron relaxation time due to competition between spin-spin and spin-lattice relaxation processes.     

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.     

A multi-frequency EPR spectroscopy approach in the detection of boson peak excitations

The influence of boson peak (BP) excitations on low-temperature spin-lattice relaxation rate of a paramagnetic center embedded in a glassy matrix is investigated in the context of multi-frequency electron paramagnetic resonance (EPR) detection. In the theoretical analysis, the transition rate of spin one-half in the presence of a phonon field is calculated within the approximation of Fermi's golden rule. Several phonon densities of states are compared, among which one originating from a model of quasi-localized vibrations has been introduced into electron spin relaxation formalism for the first time. The respective frequency dependencies of spin-lattice relaxation rates are predicted which should lead to observable effects of BP modes if a multi-frequency study at very low temperatures is performed.