Effect of oxygen diffusion on the relaxation parameters of paramagnetic centers on the surface of alumina

The present article is concerned with theoretical consideration of the effect of oxygen diffusion on the relaxation parameters of paramagnetic centers (PC) located on a surface. Proceeding from a model of dipole-dipole interaction between paramagnetic molecules of O₂ and PC that is modulated by translational diffusion motion of O₂ molecules in the volume and on surface of an adsorbent and in its pores, we give an explanation for the observed dependence of the intensity of the EPR signal on the pressure of O₂. In the present case, diffusion in the volume is the decisive factor. We also managed to explain the presence of an SHF field power threshold for the indicated phenomenon to be observed. In the calculations we used correlation functions obtained earlier for diffusion in a volume. Institute of Physicoorganic Chemistry, National Academy of Sciences of Belarus, 13, Surganov St., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 2, pp. 230–235, March–April, 1998.     

Multiphonon processes in nuclear relaxation via paramagnetic centers

We investigate the role of Orbach-Aminov multistage phonon processes in nuclear spin-lattice relaxation via paramagnetic centers for ions with 1/2 spin in the absence of splitting by the crystal field.Lenin State Pedagogical University, Moscow. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 38, No. 10, pp. 1071–1076, October, 1995.     

Random distribution of paramagnetic centers in the nuclear spin-lattice relaxation

A numerical solution is presented for the differential equation governing the nuclear spin-lattice relaxation via paramagnetic centers for spherically symmetric spin-diffusion constantD and direct relaxation transition probabilityC in the one-paramagnetic-center approximation. An interpolation function is given which reproduces the computedT ₁ values within ±5% for both the rapid diffusion and diffusion-limited cases. The introduction of a random distribution of the paramagnetic centers over the sample causes the relaxation to occur as exp(?at ^h ) with 0.5<h<1.0 forβ=(C/D)^1/4<R _av=the average radius of the influence spheres. This differs from the experimentally observed exp(?a ₁ t) behaviour. However, the random distribution seems to explain the difference between the theoretically calculated fluorine spin-diffusion in CaF₂ and that extracted from experimental NMR data by using the uniform-distribution model.     

Nonequilibrium spin states and tunnel paramagnetic centers in copper oxide CuO

It is shown that the formation of tunnel paramagnetic centers — triplet spin centers with a strongly different adiabatic potential in different spin states — can form in copper oxides based on CuO clusters. The results of measurements of the magnetization and magnetostriction of CuO single crystals are reported. They attest to the presence of nonequilibrium spin states and confirm the results obtained in the model of tunnel paramagnetic centers. Fiz. Tverd. Tela (St. Petersburg) 39, 474–482 (March 1997)     

Muon spin relaxation studies of extremely concentrated paramagnetic electrolyte solutions

The diamagnetic signal in aqueous solutions of non-reacting salts arises from muons substituted for protons in water molecules. For concentrated solutions of paramagnetic salts, muon spin relaxation results from the strong dipolar and scalar interactions between the paramagnetic ion and the muon. Information on dynamic and structural aspects of such solutions is derived from measurements of the transverse relaxation rate as a function of applied field over a wide range. Data are presented for concentrated solutions of Mn(NO₃)₂ and solutions of composition Mn _x Ca_(1–x (NO₃)₂·6H₂O.     

Outer-sphere nuclear spin relaxation in paramagnetic systems: a low-field theory

A low-field theory for paramagnetic relaxation enhancement (PRE), appropriate for the outer-sphere relaxation, is presented for the electron spin quantum number S = 1, 3/2, 2, 5/2, 3 and 7/2. The theory is used to calculate the PRE at low magnetic field, as a function of the translational diffusion coefficient, for various values of the electron spin quantum number, for small and fairly large values of the static zero-field splitting (ZFS), and for a given set of parameters determining the electron spin relaxation. We have found earlier that the static ZFS has a profound influence on the electron spin relaxation; such effects are also evident in the present study. Comparisons are made with other existing models for the outer-sphere PRE, and significant differences are found for slowly diffusing systems with large ZFS. The theory is also used to obtain a novel interpretation of experimental data for an acetone solution of a Mn(III) complex.     

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.     

Electric manipulation of spin relaxation using the spin Hall effect

Using the spin Hall effect, magnetization relaxation in a Ni_{81}Fe_{19}/Pt film is manipulated electrically. An electric current applied to the Pt layer exerts spin torque on the entire magnetization of the Ni81Fe19 layer via the macroscopic spin transfer induced by the spin Hall effect and modulates the magnetization relaxation in the Ni81Fe19 layer. This method allows us to tune the magnetization dynamics regardless of the film size without applying electric currents directly to the magnetic layer.     

The reverse shift of the EPR line of paramagnetic centers coupled to species with a fast paramagnetic relaxation

The EPR spectrum of the spin 1/2 paramagnetic centers with a relatively slow relaxation is considered in the case when they are coupled via the Heisenberg exchange interaction to partners which have short times of the longitudinal and transverse paramagnetic relaxation. Under these conditions only the EPR line of paramagnetic centers with a relatively slow relaxation is detectable in experiment. The shape of this line is analyzed by solving numerically kinetic equations for the spin density matrix for simple model systems. Depending on a ratio between the exchange integral and the paramagnetic relaxation rates of partner spins, the EPR line shifts in opposite directions. For moderate relaxation rates, as the relaxation rates decrease, the EPR line shifts toward the gravity center of the total EPR spectrum. In the case of extremely fast relaxation, as the relaxation rates decrease, the reverse shift of the EPR line is expected, the line shifts away from the gravity center of the total EPR spectrum. This type of the non-monotonous line shift was experimentally observed for the monocrystal of [CuNd₂(C₄O₄)₄(H₂O)₁₆] · 2H₂O when relaxation rates were changed by temperature variation.     

Slow-motion theory of nuclear spin relaxation in paramagnetic low-symmetry complexes: A generalization to high electron spin

The slow-motion theory of nuclear spin relaxation in paramagnetic low-symmetry complexes is generalized to comprise arbitrary values of S. We describe the effects of rhombic symmetry in the static zero-field splitting (ZFS) and allow the principal axis system of the static ZFS tensor to deviate from the molecule-fixed frame of the nuclear-electron dipole–dipole tensor. We show nuclear magnetic relaxation dispersion (NMRD) profiles for different illustrative cases, ranging from within the Redfield limit into the slow-motion regime with respect to the electron spin dynamics. We focus on S = 3/2 and compare the effects of symmetry-breaking properties on the paramagnetic relaxation enhancement (PRE) in this case with that of S = 1, which we have treated in a previous paper. We also discuss cases of S = 2, 5/2, 3, and 7/2. One of the main objectives of this investigation, together with the previous papers, is to provide a set of standard calculations using the general slow-motion theory, against which simplified models may be tested.     

Nuclear spin relaxation in solution of paramagnetic complexes with large transient zero-field splitting

A theory for paramagnetic relaxation enhancement (PRE) in systems with S> 1 at low magnetic field is developed for the case when the fluctuations of zero-field splitting (ZFS) in the molecular frame are larger than the averaged ZFS. The validity limits of the new theory are discussed, and its performance is evaluated by comparisons with the general slow-motion approach. The relevance of the new approach for the proton PRE in aqueous solution of Ni(II) is discussed.     

Water diffusion-exchange effect on the paramagnetic relaxation enhancement in off-resonance rotating frame

The off-resonance rotating frame technique based on the spin relaxation properties of off-resonance T1rho can significantly increase the sensitivity of detecting paramagnetic labeling at high magnetic fields by MRI. However, the in vivo detectable dimension for labeled cell clusters/tissues in T1rho-weighted images is limited by the water diffusion-exchange between mesoscopic scale compartments. An experimental investigation of the effect of water diffusion-exchange between compartments on the paramagnetic relaxation enhancement of paramagnetic agent compartment is presented for in vitro/in vivo models. In these models, the size of paramagnetic agent compartment is comparable to the mean diffusion displacement of water molecules during the long RF pulses that are used to generate the off-resonance rotating frame. The three main objectives of this study were: (1) to qualitatively correlate the effect of water diffusion-exchange with the RF parameters of the long pulse and the rates of water diffusion, (2) to explore the effect of water diffusion-exchange on the paramagnetic relaxation enhancement in vitro, and (3) to demonstrate the paramagnetic relaxation enhancement in vivo. The in vitro models include the water permeable dialysis tubes or water permeable hollow fibers embedded in cross-linked proteins gels. The MWCO of the dialysis tubes was chosen from 0.1 to 15 kDa to control the water diffusion rate. Thin hollow fibers were chosen to provide sub-millimeter scale compartments for the paramagnetic agents. The in vivo model utilized the rat cerebral vasculatures as a paramagnetic agent compartment, and intravascular agents (Gd-DTPA)30-BSA were administrated into the compartment via bolus injections. Both in vitro and in vivo results demonstrate that the paramagnetic relaxation enhancement is predominant in the T1rho-weighted image in the presence of water diffusion-exchange. The T1rho contrast has substantially higher sensitivity than the conventional T1 contrast in detecting paramagnetic agents, especially at low paramagnetic agent volumetric fractions, low paramagnetic agent concentrations, and low RF amplitudes. Short pulse duration, short pulse recycle delay and efficient paramagnetic relaxation can reduce the influence of water diffusion-exchange on the paramagnetic enhancement. This study paves the way for the design of off-resonance rotating experiments to detect labeled cell clusters/tissue compartments in vivo at a sub-millimeter scale.     

Clarification of the measurement of surface spin relaxation via conduction electron spin resonance

We clarify the parameterization of the probability of transverse conduction electron spin relaxation. ?, at the surface of a metal. Using Walker's boundary condition on the transverse spin magnetization, we have calculated the ? and thickness dependence of the spin resonance linewidth. The results are discussed in simple physical terms. The recent work of Allam and Vigouroux is shown to contain errors.     

The effect of traps on the muon spin relaxation function

Summary In summary it is clear that SR in the presence of traps has led to a significant generalization of prior NMR theories of spin relaxation to include the effects of a non-stationary distribution of diffusing particles. In both the high field transverse geometry and in zero field it is possible to extract significant information regarding the concentrations and binding energies of traps, and, in the latter case, to unambiguously measure the temperature dependence of the relaxation rate to traps.At the same time it is also clear that significant problems still remain to be solved. Many of these are concerned with our present inadequate knowledge regarding the diffusion of muons in even pure materials, let alone the disordered systems upon which we have concentrated here. However, given the growth in our understanding of trapping phenomena over the past several years, it is probably not too much to hope that in another few years many of these present questions will also be answered.     

Experimental evidence of the spin lattice character of surface relaxation in CESR

By measuring spin lattice relaxation time independently of any linewidth determination, we show the spin lattice character of surface relaxation in CESR. The method is based on amplitude modulation of the microwave field and detection of the longitudinal magnetization.     

Effect of lattice relaxation on spin density of nitrogen-vacancy centers in diamond and oscillator strength calculations

Using a generalized Hubbard Hamiltonian, many-electron wavefunctions of negatively charged (NV⁻) and neutral nitrogen-vacancy (NV⁰) centers in diamond were calculated. We report the effect of symmetric relaxation of surrounding atoms on the spin density, calculated from the many electron wavefunctions in the ground and excited states. We evaluated the error, that, arises in estimation of spin density when lattice relaxation effect is neglected in Electron Paramagnetic Resonance experiment and showed that the ground state spin density distribution is accessible in outward relaxations. The computed oscillator strengths give a higher efficiency for the 1.945 eV photoluminescence (PL) line of NV⁻ with respect to 2.156 eV PL line of NV⁰ which agrees well with experiment. This result is explained based on the largest the ground state spin among available values for the NV⁻ with respect to NV⁰. The transition probability between degenerate ground and excited states slightly depends on the S _z value. Finally, we report on the electronic configurations which contribute to the ground and excited states and discuss the population variation of electronic configurations with relaxation.