H and K spin-lattice relaxation, ionic motion and Raman processes in the proton conducting KHSeO4 single crystal

The spin-lattice relaxation rates of ¹H and ³⁹K nuclei in KHSeO₄ crystals were studied in the temperature range 160-400 K. The spin-lattice relaxation recovery of ¹H nucleus in this crystal can be represented with a single exponential function, and the relaxation T₁⁻¹ curve of ¹H can be represented with the Bloembergen-Purcell-Pound (BPP) function. The relaxation process of ³⁹K with dominant quadrupole relaxation can be described by a linear combination of two exponential functions. T₁⁻¹ for the ³⁹K nucleus was found to have a very strong temperature dependence, T₁⁻¹=βT⁷. Rapid variations in relaxation rates are associated with critical fluctuations in the electronic spin system. The T⁷ temperature dependence of the Raman relaxation rate is shown here to be due to phonon-magnon coupling.     

Some peculiarities of spin-lattice relaxation of impurity rare-earth ions in crystals caused by the structure defects

The spin-lattice relaxation times for Nd³⁺ ions in yttrium-aluminum garnets (YAG) and for Yb³⁺ ions in CaF₂ in the low-temperature range have been measured. For the first system the temperature dependence of the relaxation rate is determined to a great extent by the method of sample preparation. For samples grow by the method of the horizontally oriented crystallization the dependence is described asT ₁ ^?1 =AT ⁿ ,n ? 4.7, which is an evidence of an influence of local structure disordering on the relaxation. The temperature dependence of the relaxation rate in CaF₂:Yb is also “anomalous”:T ₁ ^?1 =AT ^3.3. The results are compared with the previous data on the relaxation in similar systems, and with other cases of observation of “anomalous” temperature dependences. Different manifestations of the local crystal defects in spin-lattice relaxation are discussed.     

1H relaxation and dynamics of triphenylbismuth in deuterated solvents

ABSTRACT

¹H spin–lattice relaxation experiments have been performed for triphenylbismuth dissolved in fully deuterated glycerol and tetrahydrofuran. The experiments have been carried out in a broad frequency range, from 10?kHz to 40?MHz, versus temperature. The data have been analysed in terms of a relaxation model including two relaxation pathways: ¹H-¹H dipole–dipole interactions between intrinsic protons of triphenylbismuth molecule and ¹H-²H dipole–dipole interactions between the solvent and solute molecules. As a result of the analysis, rotational correlation times of triphenylbismuth molecules in the solutions and relative translational diffusion coefficient between the solvent and solute molecules have been determined. Moreover, the role of the intramolecular ¹H-¹H relaxation contribution has been revealed, depending on the motional parameters, as a result of decomposing the overall relaxation dispersion profile into contributions associated with the ¹H-¹H and ¹H-²H relaxation pathways. The possibility of accessing the contribution of the relaxation of the intrinsic protons is important from the perspective of exploiting Quadrupole Relaxation Enhancement effects as possible contrast mechanisms for Magnetic Resonance Imaging.     

Relaxation Behavior of Laser-Polarized Xe Gas: Size Dependency and Wall Effect of the T1 Relaxation Time in Glass and Gelatin Bulbs

Size dependency of the relaxation time T₁ was measured for laser-polarized ¹²⁹Xe gas encapsulated in different sized cavities made by glass bulbs or gelatin capsules. The use of laser-polarized gas enhances the sensitivity a great deal, making it possible to measure the longer ¹²⁹Xe relaxation time in quite a short time. The size dependency is analyzed on the basis of the kinetic theory of gases and a relationship is derived in which the relaxation rate is connected with the square inverse of the diameter of the cavity. Such an analysis provides a novel parameter which denotes the wall effect on the relaxation rate when a gas molecule collides with the surface once in a second. The relaxation time of ¹²⁹Xe gas is also dependent on the material which forms the cavity. This dependency is large and the relaxation study using polarized ¹²⁹Xe gas is expected to offer important information about the state of the matter of the cavity wall.     

NMR proton relaxation and chemical exchange in the system H16 2O/H17 2O-[2H6]dimethylsulphoxide

NMR proton relaxation rates of normal and ¹⁷O enriched water in a mixture of 68 mol% water and 32 mol% [²H₆]dimethylsulphoxide were measured for temperatures between 298 K and 183 K. In the range between 240 K and 204 K the limit of fast proton-proton exchange between H¹⁶ ₂O and H¹⁷ ₂O is not obeyed, and relaxation curves deviate from mono-exponential behaviour. By fitting the relaxation curves to a model of NMR two-phase relaxation the proton-proton exchange rate within the aqueous component could be obtained. With decreasing temperature, proton-proton exchange slows down and a residence time of about 125 ms at 215 K is found, but it becomes faster again for still lower temperatures. From the phase-averaged relaxation rates of water in the ¹⁷O enriched mixtures, the ¹⁷O induced proton relaxation rate was derived as a function of temperature. This yields the rotational correlation times of the water molecule in the mixture and the dipolar spin-lattice coupling parameter. The latter is considerably lower than the one predicted from the geometry of water.     

Linewidth-Resolved N HSQC, a Simple 3D Method to Measure N Relaxation Times from T1 and T2 Linewidths

A three-dimensional approach for measuring ¹⁵N relaxation times is described. Instead of selecting particular values for the relaxation period, in the proposed method the relaxation period is incremented periodically in order to create a 3D spectrum. This additional frequency domain of the transformed spectrum contains the relaxation time information in the T₁ and T₂ linewidths, and thus the longitudinal and transverse ¹⁵N relaxation times can be measured without determination of 2D cross peak volumes/intensities and subsequent curve fitting procedures.     

Nuclear spin relaxation of 8Li adsorbed on surfaces

Nuclear spin relaxation experiments with ⁸Li adsorbed on various surfaces provide new information in surface science which is not obtainable othervise. Both dipolar (Korringa) and quadrupolar relaxation due to diffusion are observed. However, in addition, a fast and presently not understood spin relaxation mechanism is present while dosing during the first 0.5 s the surface with polarized ⁸Li. Most strange in this respect is the fact that those ⁸Li atoms which survive depolarization through this mechanism depolarize afterwards with modest spin lattice relaxation rates. The origin of the fast spin lattice relaxation mechanism is presently unknown. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mössbauer study of spin-spin relaxation of Fe3+ ions in the presence of other paramagnetic ions

Mössbauer spectroscopy has been used to study the influence of paramagnetic ions, viz. Cu²⁺, Cr³⁺, Co²⁺ Mn²⁺, Gd³⁺ and Dy³⁺ on the spin-spin relaxation time of Fe³⁺ ions in amorphous frozen aqueous solutions. It is found that these ions shorten the relaxation time, but the effect is much smaller than suggested earlier on the basis of measurements of relaxation of Fe³⁺ in an α-Al₂O₃ matrix. It is also found that S-state ions have a greater influence on the relaxation time than other paramagnetic ions. The spectra obtained in presence of S-state impurity ions could only be fitted by allowing the individual transition probabilities to vary independently.     

〈S0〉Cs and 〈S0〉Rb relaxation in the presence of buffer gas and the spin exchange between Cs and Rb

〈S⁰〉_Rb and 〈S⁰〉_Cs relaxation is studied in the presence of buffer gas and spin exchange between Cs and Rb. Spin exchange collisions are found to equalize the relaxation rates of Rb and Cs polarization. This result is completely confirmed experimentally for the relaxation of the first diffusion mode.     

Anomalous nuclear spin–lattice relaxation of <Superscript>3</Superscript>Не in contact with ordered Al<Subscript>2</Subscript>O<Subscript>3</Subscript> aerogel

Spin–lattice relaxation of ³Не in contact with the ordered Al₂O₃ fiber aerogel has been studied at the temperature of 1.6 K in fields of 0.1–0.5 T by the pulsed nuclear magnetic resonance (NMR) method. An additional mechanism of the relaxation of ³Не in aerogels is found and it is shown that this relaxation mechanism is not associated with the adsorbed layer. A hypothesis about the influence of intrinsic paramagnetic centers on the relaxation of gaseous ³Не is proposed.     

13C and 1H nuclear spin lattice magnetic relaxation in undoped polyacetylene

Pulsed NMR spin lattice relaxation measurements on ¹³C and ¹H nuclei in undoped trans-polyacetylene have been carried out between 6 and 295 K. The results indicate that the spin lattice relaxation is due to equilibrium fluctuations of the orientational order parameter for the protons while the carbon relaxation can be attributed to their coupling to paramagnetic impurities. In this temperature range no contribution of solitons has been detected in the relaxation mechanisms.     

Observation of spin-lattice relaxations of dilute Fe3+ in MgO by Mössbauer spectroscopy

We present a method to describe the temperature dependence of emission Mössbauer spectra showing slow spin-lattice relaxations of Fe^3?+? in MgO single crystals, obtained after implantation of ⁵⁷Mn at ISOLDE/CERN. The analysis is based on the Blume-Tjon model for the line-shape of relaxing paramagnetic sextets with the spin relaxation rate, τ ^???1 as a parameter. The temperature dependent spin relaxation rate of Fe^3?+? in MgO is found to increase to ~10⁸ s^???1 at 647 K by assuming a relaxation rate of τ ^???1?< 10⁶ s^???1 at 77 K. The results are in accordance with those obtained by electron paramagnetic resonance spectroscopy demonstrating the possibility of retrieving spin-lattice relaxation rates of dilute Fe^3?+? from emission Mössbauer spectroscopy of Mn/Fe-implanted oxides.     

Proton relaxation times in 7LiCl and 6LiCl solutions

Measurements of the proton spin-lattice relaxation times have been made as a function of concentration and temperature in aqueous solutions of ⁷LiCl and ⁶LiCl. The difference in the relaxation times for two isotopic solutions of the same concentration and temperature is small, corresponding to a difference n reciprocal relaxation times of 0·004 sec^-1. c at 25°c, where c is the molarity of the solutions. This value decreases with increasing temperature. It is shown that the difference in relaxation times arises solely from the magnetic dipole interaction between the ⁷Li ion nucleus and water protons. The concept of a long-lived, rigid hydrated complex around the Li ion is shown to be inconsistent with the results.     

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.     

Effect of oxygen on the NMR relaxation properties of crude oils

Nuclear magnetic resonance relaxation measurements of bulk fluids provide a sensitive probe of the dynamics of molecular motion. Dissolved oxygen can interfere with this technique as its paramagnetic nature leads to a reduction of the paramagnetic relaxation times of the fluids. We studied this effect for the relaxation properties of crude oils that are in general characterized by a distribution of relaxation times. The samples were stock tank oils that have been exposed to air. We comparedT ₁ andT ₂ relaxation time distributions and their correlation functions of the initial (oxygenated) samples with those from the deoxygenated samples. Oxygen was removed from the oils with a freeze-thaw technique. As expected, the effect of oxygen is most apparent in oils with long relaxation times. In these oils the effect of oxygen can be described by an additional relaxation rate 1/T _1,2 ^ox to the transverse and longitudinal relaxation rates that is sample dependent but does not vary within the relaxation time distribution of the oil. Values of 1/T _1,2 ^ox for different crude oils were found to be in the range of 2.5 to 8.3 s. For crude oils that have components with relaxation times less than 100 ms, no significant oxygen effect is observed.     

33S and 17O nuclear magnetic resonance studies of aqueous methanesulfonic and trifluoromethanesulfonic acids

The ³³S and ¹⁷O NMR linewidths of trifluoromethanesulfonic acid (TFMSA) and methanesulfonic acid (MSA) decrease at lower concentrations in aqueous solution. Plots of ³³S and ¹⁷O relaxation times vs MSA concentration are linear between 8 and 0.2 M. Relaxation times at infinite dilution and the effects of temperature and decoupling are reported for MSA. Decreased concentration dependence above 8 M appears to be related to decreased ionization and substantial solvation changes. For TFMSA, a similar break is observed for ³³S relaxation above 5 M but ¹⁷O relaxation was entirely linear. For MSA, relaxation times of both nuclei are linearly correlated with the degree of ionization. For both anions, the ³³S chemical shifts are concentration independent, but downfield ¹⁷O shifts are observed at lower concentrations.     

Wall relaxation of spin polarized 129Xe nuclei

The wall relaxation of spin polarized ¹²⁹Xe nuclei is much longer in silicone coated pyrex cells than in uncoated cells. In contrast to uncoated glass cells where the wall relaxation times are unpredictable and usually only a few tens of seconds, the relaxation time of ¹²⁹Xe in silicone-coated cells is usually 20 minutes or longer.     

The optical conductivity of free carriers in GaAs

The optical conductivity of free electrons in polar semiconducting compounds has recently been calculated by use of a generalized Boltzmann equation derived from the equation of motion of the quantum density matrix. This reduces to the quasi-classical Boltzmann transport equation in the low frequency limit: the optical conductivity thus obtained spans a spectral range from around 30cm^?1 to 1.2 × 10⁴cm^?1 in GaAs. In this paper, the optical conductivity is calculated for GaAs as a function of carrier concentration in terms of a frequency dependent relaxation time which reduces to the usual relaxation time in the limit of low frequencies and an elastic scattering mechanism. The low frequency limit of the relaxation time is used to estimate the mobility as a function of carrier concentration. The frequency dependent relaxation time is given for GaAs at 298 K over the spectral region from 45 cm^?1 to 2.3 × 10³cm^?1 for carrier concentrations from 3.4 × 10¹⁵cm^?3 to 8.7 × 10¹⁸cm^?3.     

Laser-induced temporal and wavelength resolved spectroscopy of the 2Σ−-2Π and 2Δ-2Π systems of CH and CD isolated in rare gas matrices

The relaxation dynamics of matrix isolated CH and CD have been studied using laser-induced time and wavelength resolved spectroscopy. Vibrationally relaxed B(0′-0″) fluorescence occurs following laser excitation both above and below the gas phase dissociation limit. The vibrational relaxation rate in the B state of CH is found to be 4.6 × 10⁶ sec^?1 while the corresponding rate in CD is 5.7 × 10⁵ sec^?1. The primary accepting mode in the relaxation process is consistent with rotation.     

19F N.M.R. and 127I N.M.R. and N.Q.R. study of the molecular motions and deformations of iodine heptafluoride in its solid phases

In solid IF₇, ¹⁹F and ¹²⁷I N.M.R. and ¹²⁷I N.Q.R. absorption line shapes, frequencies and relaxation times have been studied from the melting temperature down to 56 K. Two new solid-solid transitions have been found at 180 K and 96 K in addition to the one already known at 153 K. The two high temperature phases are shown to be plastic. The fast molecular rotations and the slow molecular diffusion are studied from ¹⁹F and ¹²⁷I relaxation times. In the ordered phases, an analysis of the ¹⁹F second moments and longitudinal relaxation times shows the existence of a fast intramolecular exchange between axial and equatorial fluorine atoms, together with a much faster reorientation about the D ₅ axis. The characteristic times of these two motions are obtained and a mechanism for the exchange process is proposed. The chemical shift values of ¹²⁷I, the temperature dependence of the N.Q.R. frequencies and of the N.Q.R. relaxation times of ¹²⁷I, as well as the dipolar energy relaxation times have been measured and are discussed.