Nuclear spin-lattice relaxation of impurities in ferromagnetic iron

Due to the development of Green's function method the calculation of the nuclear spin-lattice relaxation time of impurities in ferromagnets has become feasible in the last years. We present the result of calculations for allsp andd impurities in ferromagnetic iron. The calculations are based on the density functional formalism. They well, reproduce the experimental trend of the relaxation timeT ₁ for bothsp andd impurities. By decomposing the relaxation rate into various contributions, we explain the observed systematic behavior ofT ₁ T in terms of the local electronic structure.     

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.     

Molecular motions in chloramphenicol studied by35Cl nuclear quadrupole and1H nuclear magnetic resonance spectroscopy

The³⁵Cl nuclear quadrupole resonance (NQR) frequency (v_Q), nuclear quadrupole spinlattice relaxation time (T_1Q),¹H nuclear magnetic resonance second moment (M₂) and nuclear magnetic spin-lattice relaxation timeT ₁) were measured for polycrystalline chloramphenicol (drug) as a function of temperature. Hindered rotation of the CHC1₂ group and the phenyl ring was detected, the relevant activation energies were determined. The rotations are discussed in detail.     

The1HT 1 study of the influence of clay addition on Portland cement hydration

Effects of addition of three standard clay minerals, Na-montmorillonite, illite and kaolinite, on Portland cement hydration properties were studied. The¹H spin-lattice relaxation of exchangeable water was monitored during hydration time and the data were processed by spin-grouping analysis. The values and evolution dynamics of both resolvedT ₁ components and corresponding magnetization fractions show that each day mineral lowers the fluidity of Portland cement paste and accelerates its hydration in dormant. In advanced stages of hydration, the Na-montmorillonite provides the accelerating influence, while the kaolinite exhibits the retarding effect. The final values of gel pores to capillaries percentage fractions ratio indicate a slightly lower porosity of samples with Namontmorillonite and a higher porosity of pastes with the same percentage of illite or kaolinite, regarding to the pure hardened Portland cement.     

Paramagnetische Relaxation und Phonon-Engpaß im Terbium-Äthylsulfat

The magneto-optical Faraday effect was used to study the spin-lattice relaxation in in the terbium ethyl sulfate. The effective spin-lattice relaxation timeT _eff was measured in the temperature range 1,4≦T≦3,5 °K and for magnetic fields of 1000, 1500 and 2000 Oe.T _eff depends on the initial disturbance of the thermal equilibrium between the spin-system and the lattice. There has been identified a phonon bottleneck in the terbium ethyl sulfate.     

An NMR thermometer for cryogenic magic-angle spinning NMR: the spin-lattice relaxation of (127)I in cesium iodide

The accurate temperature measurement of solid samples under magic-angle spinning (MAS) is difficult in the cryogenic regime. It has been demonstrated by Thurber et al. (J. Magn. Reson., 196 (2009) 84-87) [10] that the temperature dependent spin-lattice relaxation time constant of ⁷⁹Br in KBr powder can be useful for measuring sample temperature under MAS over a wide temperature range (20–296 K). However the value of T₁ exceeds 3 min at temperatures below 20 K, which is inconveniently long. In this communication, we show that the spin-lattice relaxation time constant of ¹²⁷I in CsI powder can be used to accurately measure sample temperature under MAS within a reasonable experimental time down to 10 K.     

Phonon-Engpaß und sein Einfluß auf die paramagnetische Relaxation

The coupled spin-lattice and lattice-bath differential equations are solved numerically for the special case of terbium ethyl sulfate. The relaxation decay shows non-exponential behaviour if the lifetime τ of the phonons in direct contact with the spin-system is equal or greater thanT ₁/b.T ₁ is the spin-lattice relaxation time andb the ratio of the specific heats of the spin-system and the phonons in contact with the spin-system. The effective (measured) relaxation timeT _eff depends on the initial disturbance of the spin-system. In a second paper measurements are published which show these predicted effects. In these experiments there has been found a severe phonon bottleneck in the terbium ethyl sulfate.     

Factors Affecting Early-Age Hydration of Ordinary Portland Cement Studied by NMR: Fineness,Water-to-Cement Ratio and Curing Temperature

The aim of the present study was to apply nuclear magnetic resonance (NMR) relaxation measurements for understanding the microstructure evolution of cement paste during hydration. Ordinary Portland cement powder was mixed with double-distilled water, and hydration process was analyzed via ¹H proton NMR spin–spin relaxation time. In order to induce strong modification of the rate of hydration, water-to-cement ratio, curing temperature and cement fineness were varied. The evolution of the NMR spin–spin relaxation time, T ₂, of hydrating water versus the hydration time was monitored from the very first few minutes after the mixing up to several hours. Authors' address: Marcella Alesiani, Department of Physics, University La Sapienza, Piazzale Aldo Moro 5, 00185 Rome, Italy     

Nuclear spin-lattice relaxation in54Mn-MnCl2.4H2O and lower dimensional magnetic systems

We report on nuclear spin-lattice relaxation studies on⁵⁴Mn-MnCl₂.4H₂O and 2-dimensional⁵⁴Mn-Mn(COOCH₃)₂.4H₂O. In the former crystal, we find that at the lowest temperatures a direct process, normally thought of as forbidden, becomes the mechanism for relaxation. In lower dimensional systems the relaxation might be expected to be relatively fast and indeed in the acetate the relaxation timeT ₁ is ≈1000 s in an applied field of 0.2 T for the Mn2 site and is much shorter at lower fields. In 1-dimensional⁵⁴Mn-(CH₃)₄NMnCl₃(TMMC) a significant γ-ray anisotropy is observed on cooling indicating thatT ₁ is also short in this system. The shortness ofT ₁ in the lower dimensional systems suggests that they may be suitable hosts for on-line experiments.     

Nuclear spin-lattice relaxation in the triply rotating frame and ultraslow molecular motions in solids

A method for measuring nuclear magnetic spin-lattice relaxation in solids in the effective field H_e3 acting in the triply rotating frame (TRF) is described. The method advances the previously described techniques whereby nuclear magnetic resonance and relaxation in the rotating (RF) and doubly rotating frames (DRF) are measured directly. In the present work, the RF and DRF are employed for suppressing the secular part of nuclear dipole-dipole (DD) interactions in the first two orders. As a result, the higher-order DD interactions (four- and five-particle ones) were separated, and their contribution to the nuclear spin-lattice relaxation in the TRF was studied experimentally. The experiments were carried out on protons in polycrystalline benzene. With the introduced technique, an overall spin-lattice relaxation decay in the TRF was recorded continuously during a single radio-frequency pulse with a length not exceeding 1 s. The contribution of multiproton nonsecular DD interactions to the proton spin-lattice relaxation in the TRF was observed selectively as a pronounced local minimum in the temperature dependence of the relaxation timeT _1ϱϱϱ. This contribution corresponds to ultraslow motion of benzene molecules with a rate about γH_e3 ≈ 2π · (10¹-10³) s^-1 and is determined quantitatively by specific correlation functions corresponding to the multiparticle nonsecular DD interactions of protons. The prospects of using this method for studying ultraslow atomic and molecular dynamics in solids are discussed.     

Nuclear quadrupole resonance and thermally activated molecular mobility in solids: Reorientations of symmetric molecular species and pseudorotation in trigonal-bipyramidal molecules

The specific features revealed in the behavior of temperature dependences of the spin-lattice relaxation time t ₁ of quadrupole nuclei involved in different types of thermally activated motions in crystals have been analyzed under the assumption that there exists a temperature dependence of the activation energy of motion. An expression for the spin-lattice relaxation rate has been obtained. This expression includes the effect under consideration and provides an adequate explanation for numerous anomalies in the behavior of the experimental dependences t ₁(T), which were revealed in the case of the motion of molecular fragments with a relatively large volume. A nontraditional method for evaluating the activation energy of motion under these conditions has been proposed.     

Nuclear spin-lattice relaxation in the mixed state of superconducting niobium

Pulsed NMR measurements of the spin-lattice relaxation timeT ₁ have been carried out in niobium metal, in order to investigate the elementary excitation spectrum in the superconducting mixed state. The dependences ofT ₁ on temperature, external field, and mean free path were determined. The results below ～5°K were in agreement with the theory of field-induced gapless superconductivity. The best fit was obtained with a scale factor 0.35±0.2, in agreement with recent ultrasonic attenuation results. Anomalously fast relaxation was observed above ～5°K, which could not be interpreted in terms of the present theory of thermal vortex fluctuations.     

14N NMR study and Landau theory of phase transitions in [N(CH3)4]2ZnI4

The¹⁴N NMR spectra and spin-lattice relaxation timeT ₁ of [N(CH₃)₄]₂ZnI₄ have been studied between room temperature and 200 K. Two phase transitions atT _c 1=255 K and atT _c 1=217 K are observed. The¹⁴N NMR lineshape andT ₁ data suggest that the intermediate phase is commensurate rather than incommensurate in spite of the presence of a Lifshitz invariant in the expansion of the free energy density in powers of the order parameter. We also discuss the phenomenological theory of structural phase transitions in [N(CH₃)₄]₂ZnI₄.     

Spin-orbit coupling,spin-lattice relaxation,and spin-memory studies ofF-center-molecular-ion pairs in alkali halides

Summary The spin-orbit parameter Δ, spin-lattice relaxation timeT ₁, and spin-mixing parameter ɛ ofF _H(OH⁻) andF _H(CN⁻) centers in several alkali halides have been studied with magnetic circular dichroism at ∼2 K. A close comparison of the experimental results before and after optically induced association of theF center with the molecular ion has been made. In crystals of NaCl structure the negative spin-orbit parameter Δ changes little betweenF andF _H centers in the same host. For CsCl and CsBr two values of Δ have been derived forF _H(CN⁻) centers with axis parallel or perpendicular to the magnetic field. In all studied systems, the spin-lattice relaxation timeT ₁ is already shorter before aggregation compared toF formation. The spin-mixing parameter ɛ decreases slightly forF _H(OH⁻) compared toF centers, while it increases drastically forF _H(CN⁻) defects and reaches its maximum possible value ɛ=0.5 in cesium halides. First attempts to interpret these magneto-optical results will be presented. In honour of Prof. Fausto Fumi on the occasion of his retirement from teaching.     

Spin-lattice relaxation in the rotating frame and extreme slowing-down at the antiferroelectric transition in copper formate tetrahydrate

The effect on the temperature behavior of the spin-lattice relaxation rates in laboratory and rotating frames in presence of extreme slowing-down of the critical fluctuations in an Ising-type system is discussed. Proton spin-lattice relaxation measurements of T₁ and T_1? in water-deuterated copper formate tetrahydrate are presented. The data shown that the anomalous behavior of the proton T_1? in the neighbourhood of the antiferroelectric phase transition recently observed by Zumer and Pir? in the ordinary crystal cannot be ascribed to the critical slowing-down of the water molecules. A possible interpretation on the basis of a mechanism of creation and annihilation of paramagnetic excitons is discussed.     

Homogeneous FID signals in polypyrroles:T 1-estimate from a two-pulse sequence in homogeneous systems

Several experiments using pulse electron spin resonance (ESR) equipment reveal that homogeneous free induction decay (FID) signals are given by electron spins in polypyrrole (PPy). FID signals obtained from PPy are accurately fitted via single-exponential curves, thus indicating that PPy can be used as a standard sample for several experiments with pulse ESR. We particularly pay attention to the nutation phenomena resulting from two-pulse irradiation (θ-t−2θ-t) in the homogeneous systems. The analysis by the vector model suggests that the nutation curves are affected by spin-lattice relaxation. Such a tendency is actually observed for two types of PPy used as examples ofT ₁ >T ₂ andT ₁ ≈T ₂. Thus the fitting over the nutation curve can be utilized for estimatingT ₁. We particularly point out that such a procedure can be advantageously performed for electron spins with a short spin-lattice relaxation time.     

Paramagnetische Relaxation in Holmium- und Dysprosium-Äthylsulfat

The magneto-optical Faraday effect was used to measure the spin-lattice relaxation timeT ₁ of the rare earth ions Ho and Dy in the ethyl sulfate in the temperature range 1.4≦T≦2.15°K and for magnetic fields between 100 and 5300 oersteds. The magnetic field was pulse modulated and the approach to equilibrium in the spin populations was studied. The measured dependence ofT ₁ on the temperature is in good agreement with theory. Cross-relaxation processes have been identified in the holmium ethyl sulfate.     

NMR and NQR studies in high-T c oxides: YBa2Cu3O y (6.0≤y≤6.91)

The NQR and NMR techniques have been utilized to characterize the local oxygen coordination of inequivalent Cu sites and the electronic properties in both the normal and superconducting states of YBa₂Cu₃O_y (6.0<-y≤6.91). The distinct NQR lines associated with the different oxygen-coordinated Cu sites, hence the locally differentiated charged states, have been observed. The degree of charge differentiation at the Cu(2) plane sites was found to be increased with decreasingy from 6.91, which might be related with the decrease ofT _c. An anomalous temperature dependence of Cu nuclear spin-lattice relaxation timeT ₁ has been observed for both the Cu(1) chain and Cu(2) plane sites fory=6.91 and it is discussed in connection with antiferromagnetic spin fluctuations in the normal state.     

Proton spin-lattice relaxation by critical polarization fluctuations in KH2PO4

The observed anomalous decrease in the proton spin-lattice relaxation timeT ₁ on approaching the Curie point in a rather pure KH₂PO₄ single crystal is explained by magnetic dipolar coupling to the ferroelectric mode. The isolated “non-interacting” O?H...O proton flipping time is estimated from theT ₁ data as τ=0.66·10^?12 sec for the paraelectric phase and τ=2.24·10^?12 sec for the ferroelectric phase, in good agreement with the results obtained from other methods.     

NMRON studies of the antiferromagnetic and paramagnetic phases of54Mn-MnCl2 · 4H2O

Pulsed NMRON, CW NMRON and thermal NMR-NO methods have been utilized to study⁵⁴Mn-MnCl₂ · 4H₂O. The⁵⁴Mn spin-lattice relaxation timeT ₁ in zero applied field has been measured between 35 and 90 mK in the antiferromagnetic phase. Above 65 mK the dominant relaxation mechanism is a Raman process with the electronic magnons, but at lower temperatures a direct process takes over. NMRON has been observed for the first time in the paramagnetic phase, and a line width of 300 kHz, with both homogeneous and inhomogeneous contributions, is observed. In the antiferromagnetic phase the line width is 35 kHz, and there are also homogeneous and inhomogeneous contributions. The dependence ofT ₁ for the⁵⁴Mn spins on field and temperature was studied in the paramagnetic phase. AT ₁ minimum centred atB ₀=2.64 T was observed. The hyperfine parameter <⁵⁴ AS>/h=−513.6(3) MHz in the paramagnetic phase, and comparison with the value in the antiferromagnetic phase gives 0.013(1) for the zero point spin deviation.