Proton spin-lattice relaxation in aqueous ionic solutions

The proton spin-lattice relaxation time, T ₁, has been measured for aqueous solutions of sodium, potassium, rubidium and magnesium chlorides up to a concentration of about 4N at 25°c. The sodium and the magnesium chloride solutions were also measured at 60°c and 100°c. The variation of 1/T ₁ is not linear with concentration, at least above about ¼N, in contrast with previous reports [1, 2]. The behaviour depends markedly on the nature of the salt and on the temperature. It is shown that almost the whole of the variation of T ₁ as compared with that of water can be directly and simply related to the corresponding changes in the shear viscosity of the solutions. It is noted that the viscosity correction is better the higher the temperature of the solution.     

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.     

On the influence of covalence on paramagnetic spin-lattice relaxation

The paramagnetic spin-lattice relaxation times of an isolated Ir⁴⁺ ion inserted in the crystalline lattice (NH₄)₂PtCl₆ are computed. The computation is carried out for a Van Vleck relaxation mechanism taking account of the possibility of the formation of molecular orbits. It is shown that the effect of covalence in this case can be taken into account effectively in terms of the modified quantities ¯r² and ¯r⁴, the mean square and mean fourth power of the electron radius. The results of calculations agree better with experiment as compared to estimates obtained without using molecular orbitals.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii Fizika, No. 7, pp. 48–51, July, 1971.The author is deeply grateful to L. K. Aminov for numerous valuable comments, as well as to I. V. Ovchinnikov and B. Z. Malkin for useful discussions of the results of the research.     

Study of the effect of a low-frequency magnetic field on the spin-lattice relaxation in water and in aqueous solutions

The spin-lattice relaxation times in water and NaCl aqueous solutions in a low-frequency magnetic field have been measured on natural-concentration ¹⁷O nuclei. The activation energies have been calculated. The differences in the temperature dependences of the spin-lattice relaxation time and the changes in the relaxation with the magnetic field frequency are established.     

Dielectric relaxation in aqueous solutions and suspensions

A method is proposed for measuring the relaxational dielectric losses of liquids at radio frequencies on a background of large conductivity losses. The absorption of the electromagnetic field energy is explained by structural relaxation, i.e., by the processes of formation and destruction of clusters.Translated from Isvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 81–85, February, 1975.     

Calculation of spin-lattice relaxation times

A general expression is found for the probability for a direct (single-phonon) relaxation transition for arbitrary symmetry of the surroundings of a paramagnetic ion having an effective spin of S = 1/2. The expression is compared with experiment for the case of tetragonal symmetry. Since certain approximations frequently used in the calculations are not used here, a markedly improved agreement is found with the experimental relaxation times.Translated from Izvestiya VUZ. Fizika, No. 2, pp. 36–39, February, 1970.     

Chemical relaxation spectrometry in aqueous surfactant solutions

Chemical Relaxation Spectrometry is the term coined by Eigen to describe the range of experimental techniques which enable the study of the kinetics of fast reactions in solution in the time range 1–10⁻¹⁰s. This paper reviews the progress in the application of some of these techniques as well as the interpretation of the data in various surfactant solutions since the pioneering work in the early 1970's.     

NMR relaxation of protons in tissues and other macromolecular water solutions

Nuclear magnetic resonance (NMR) longitudinal (T₁) and transverse (T₂) relaxation parameters have been evaluated for protein solutions, cellular suspensions and tissues using both data from our laboratory and the extensive literature. It is found that this data can be generalized and explained in terms of three water phases: free water, hydration water, and crystalline water. The proposed model which we refer to as the FPD model differs from similar models in that it assumes that free and hydration water are two phases with distinct relaxation times but that T₁ = T₂ in each phase. In addition there is a single correlation time for each rather than a distribution as assumed in most other models. Longitudinal decay is predicted to be single exponent in character resulting from a fast exchange between the free and hydration compartments. Transverse decay is predicted to be multiphasic with crystalline (T₂ 10 μsec), hydration (T₂ 10 sec) and free (T₂ 100 sec) water normally visible. The observed or effective transverse relaxation times for both the hydration and free water phases are greatly affected by the crystalline phase and are much shorter than the inherent relaxation times.     

Proton spin-lattice relaxation in MBDBP

We have measured the proton spin-lattice relaxation rate R in 4,4′-methylenebis(2,6-di-t-butylphenol) (MBDBP) and MBDBP-OD (deuteriated hydroxyl proton) between 88 K and 380 K. The experimental results are compared with those from a previous study in the closely related but simpler molecule 4-methyl-2,6-di-t-butylphenol (MDBP). The present experiment is analysed in terms of relaxation resulting from intramolecular reorientation modulation of the proton spin-spin interaction. This intramolecular reorientation involves different combinations of superpositions of methyl, t-butyl, aromatic ring and hydroxyl group reorientation and a discussion is presented concerning the effects on the relaxation of superimposing these motions. The MBDBP-OD data is best fitted with the assumption that only methyl and aromatic ring reorientations occur. In MBDBP it is found that, in addition, an OH flip-flop motion is superimposed on the aromatic ring reorientation.     

The spin-lattice relaxation mechanism in the phosphorescent triplet state

A new mechanism is proposed for spin-lattice relaxation (SPL) in the phosphorescent triplet state of a molecule that has no inversion point. The mechanism is based on the fact that the internal spin-orbital interaction in a molecule allows the transition between spin sublevels of the triplet induced by the variable crystal field of the lattice.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 27–31, May, 1978.     

Proton spin-lattice relaxation in iron fluosilicate

Proton T₁ of FeSiF₆·6H₂O is proportional to exp (Δ/kT)at liquid helium temperatures, with Δ ≈ D - 3E. We find the crystal field splitting of the Fe²⁺ ion in this salt to be D = (12.2 ± 1.0) cm^-1 using E = 0.54 cm^-1.     

Deuteron spin-lattice relaxation in ammonium hexachlorometallates

Deuteron spin-lattice relaxation via the motion-dependent part of the electric quadrupole interaction is discussed in partly and fully deuterated ammonium ions of ammonium hexachlorometallates. The dominant motion at temperatures T>50K is normally 120 degrees reorientations of the ammonium ions. In some hexachlorometallates the instantaneous equilibrium directions of the nitrogen-hydrogen vectors make a certain angle Delta with the metal-nitrogen vectors and they appear in groups of six near each metal-hydrogen vector. Each N-D vector jumps between the six directions of one group and this motion (called limited jumps) dominates the deuteron relaxation at lower temperatures. In some samples one direction of each group seems to become more populated than the others when the deuteration degree exceeds a certain value and the ammonium ions become ordered. A model is derived for the relaxation rate in the absence of tunnelling splittings, which includes the effects of reorientations and limited jumps also in the ordered structure, where the limited-jump rate of a N-D vector to the preferred direction, r(p), differs from that to the nonpreferred direction, r(n). The obtained relaxation rate depends, in addition to the angle Delta, also on the ratio d=r(n)/r(p). The effect of d is discussed and estimates for it are presented on the basis of earlier experiments. The recent model for the deuteron relaxation in NH(3)D(+) ions, including the effect of proton tunnelling, is shortly reviewed. At lowest temperatures the motional rates can be dominated by corresponding incoherent tunnelling and the rate of the incoherent tunnelling contributing to limited jumps is argued to be clearly larger than that of the incoherent tunnelling contributing to approximately 120 degrees rotations.     

Proton spin-lattice relaxation time of hydrated gelatin

In this work we obtain a model to describe the relaxativity of water molecules, adsorbed on macromolecules, as a function of the concentration. Excellent agreement with experimental data was obtained. The model allows us to estimate the adsorption energy of water molecules on different sites of the macromolecules.     

Nuclear spin-lattice relaxation of impurities in iron

Up to intermediate atomic numbers, the new results ofab initio calculations are in good agreement with observed high-field relaxation rates, whereas model calculations for transition elements lead to serious discrepancies in some cases. So far there is no consistent theoretical picture explaining the strongly enhanced relaxation at low applied magnetic fields. A first chapter discusses the evaluation of relaxation constants from NO experiments.     

Nuclear spin-lattice relaxation in germanium single crystals

The temperature dependence of the spin-lattice relaxation time corresponding to the inelastic scattering of phonons by the⁷³Ge quadrupole moment in Ge single crystals is calculated in the framework of the adiabatic bond charge model. The results obtained agree with the experimental data.     

Proton dipolar spin-lattice relaxation in hexagonal ice

The ultraslow motion of defects in high purity hexagonal H₂O ice has been studied by proton dipolarT _1D measurements in the strong collision limit, using the Jeener technique. The obtained NMR correlation times agree rather well with both the Schottky H₂O diffusion timest _s=r ²/6D and the deuteron correlation times in D₂O ice, suggesting that Schottky rather than interstitial diffusion dominates spin-lattice relaxation in both H₂O and D₂O ice.On leave of absence from University of Ljubljana, Institute J. Stefan.     

Nuclear spin-lattice relaxation in single domain particles

Small precipitates of bcc Fe were made by tempering foils of Cu₆₉Au₃₀Fe₁ and Cu₆₇Au₃₀Fe₃. By Mö\bauer source experiments using⁵⁷Fe, hyperfine fields and particle sizes, deduced from their superparamagnetism, were investigated. Nuclear spin lattice relaxation (SLR) was measured by nuclear orientation and thermal cycling method. We found an increase in SLR rates with decreasing external magnetic field and a drastic increase with decreasing particle size. This may be explained by a uniformly fluctuating particle magnetization.     

Rb87 spin-lattice relaxation in RbMnF3

Nuclear spin-lattice relaxation rate measurements of Rb⁸⁷ in the isotropic antiferromagnet RbMnF₃ have been performed from 27 to 500°K. Both the high temperature value of the relaxation rate and its temperature dependence are well explained by a theoretical calculation essentially based on Moriya's theory.