Velocity autocorrelation spectra of fluid in porous media measured by the CPMG sequence and constant magnetic field gradient

Carr-Purcell-Meiboom-Gill (CPMG) train of radiofrequency pulses applied to spins in the constant magnetic field gradient is an efficient variant of the modulated magnetic field gradient spin echo method, which provides information about molecular diffusion in the frequency domain instead of in the time domain as with the two-pulse gradient spin echo. The frequency range of this novel technique is broad enough to sample the power spectrum of displacement fluctuation in water-saturated pulverized silica (SiO2) and provides comprehensive information about the molecular restricted motion as well as about the structure of the medium.     

Observation of a new coherent transient in NMR — Two-pulse nutational stimulated echo in the angular distribution of gamma-radiation from oriented nuclei

A new coherent transient in NMR, the two-pulse nutational stimulated echo is reported for the ferromagnetic system⁵⁰CoFe, observed by monitoring the nuclear spin dynamics as a function of the second pulse duration via anisotropic gamma quanta from thermally oriented radioactive nuclei,⁶⁰Co. The mechanism of echo formation under strong Larmor inhomogeneous broadening and the secondary but important role of inhomogeneity associated with the rf amplitude (Rabi freqeuncy) due to skin-effect are investigated via the method of concatenation of perturbation factors in the statistical tensor formalism. For those experiments performed on time scales short compared with irreversible relaxation the theoretical predictions and subsequent experimental time-domain signals are in excellent accord. Remarkable constancy of amplitude of the new gamma-detected two-pulse echo with increase of interpulse time interval is observed, the longitudinal relaxation being manifest in the off-echo signals. Comparisons are made with NMRON four-pulse stimulated off-echo decay (analogous with conventional NMR three pulse stimulated echo) which is also sensitive to longitudinal relaxation, and with three-pulse on-echo decay (analogous with conventional NMR two-pulse Hahn echo) which measures transverse relaxation.     

Electron spin-echo envelope modulation at S-band. 3: Analysis of nuclear quadrupole interaction effects

In the present paper the nuclear modulation of electron spin echo signals at S-band is investigated in the case of interacting nuclei with a quadrupole moment high enough to cause nuclear quadrupole couplings not negligible with respect to the nuclear Zeeman and dipolar hyperfine couplings. Both the two-pulse and three-pulse electron spin echo envelope modulation (ESEEM) due to²⁷Al and¹⁴N are simulated at different values of the nuclear quadrupole coupling by numerical diagonalization of the nuclear Hamiltonians. The behavior of their amplitude and periods is discussed on the basis of the ratios between the strengths of the nuclear quadrupole interaction and the nuclear Zeeman and the dipolar hyperfine interactions. The interpretation of their trends in terms of the eigenfunctions and eigenvectors of the nuclear Hamiltonians is carried out by using analytical equations obtained by perturbation approaches. First order perturbation treatments for integer and half-integer nuclear spin quantum numbers are developed when the nuclear quadrupole coupling is the main interaction. A discussion on the limits of the interpretation based on the perturbation approach is also given by comparing the magnitude Fourier transform of the patterns calculated by exact diagonalization and analytical equations.     

Electron spin-echo experiments in photo-excited triplet states in an external magnetic field

Electron spin-echo experiments in the photo-excited triplet states of quinoxaline-d₆ and naphthalene-d₈ at 1·2 K in an external magnetic field are presented. These include two-pulse Hahn echoes, three-pulse stimulated echoes and Carr-Purcell pulse-echo trains. The decay of the Hahn and stimulated echoes as a function of pulse interval yields measures of the spin relaxation times. Furthermore, the Hahn echo is used to obtain E.P.R. line shapes and the dynamics of the triplet sublevel populations. The angular dependence of the Hahn echo is also investigated. The Hahn echo decay time and decay modulation suggest the kind of role played by nuclear spins in the loss of electron spin phase coherence. Some promising characteristics of the pulse method are discussed.     

Spin echo of a single electron spin in a quantum dot

We report a measurement of the spin-echo decay of a single electron spin confined in a semiconductor quantum dot. When we tip the spin in the transverse plane via a magnetic field burst, it dephases in 37 ns due to the Larmor precession around a random effective field from the nuclear spins in the host material. We reverse this dephasing to a large extent via a spin-echo pulse, and find a spin-echo decay time of about 0.5 micros at 70 mT. These results are in the range of theoretical predictions of the electron spin coherence time governed by the electron-nuclear dynamics.     

Anomalous hyperfine field and orbital moment of cobalt in RCo2; R = Pr,Nd, Sm,Gd, Tb,Dy, Ho,Er and Tm

⁵⁹Co spin echo NMR spectra in the magnetically ordered phase of the MgCu₂ type RCo₂ compounds (R = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er and Tm) have been observed. For the RCo₂ with the easy direction of magnetication parallel to the 〈011〉 or 〈111〉 direction, the ⁵⁹Co hyperfine fields at two magnetically inequivalent Co sites are found to be antiparallel, revealing a large anisotropy in the ⁵⁹Co hyperfine field. The results are discussed in terms of a large and anisotropic orbital moment of Co. The transferred hyperfine field due to rare earth spins is estimated from well resolved satellite lines observed in Tb_1?xY_xCo₂. The nuclear quadrupole splitting in the magnetically ordered phase is found to be always larger than that in the paramagnetic phase.     

Optical pump-probe measurements of local nuclear spin coherence in semiconductor quantum wells

We demonstrate local manipulation and detection of nuclear spin coherence in semiconductor quantum wells by an optical pump-probe technique combined with pulse rf NMR. The Larmor precession of photoexcited electron spins is monitored by time-resolved Kerr rotation (TRKR) as a measure of nuclear magnetic field. Under the irradiation of resonant pulsed rf magnetic fields, Rabi oscillations of nuclear spins are traced by TRKR signals. The intrinsic coherence time evaluated by a spin-echo technique reveals the dependence on the orientation of the magnetic field with respect to the crystalline axis as expected by the nearest neighbor dipole-dipole interaction.     

The effect of spectral diffusion on the phase coherence of phosphorescent triplet spins

We have made a systematic study of the effect of spectral diffusion on the phase coherence of phosphorescent triplet spins. The effect is caused by time dependent hyperfine interactions with surrounding nuclear spins, which make the resonance frequencies of the spin-packets vary in time. From the behaviour of the spin echo signals we derive characteristic parameters for these frequency instabilities.     

Spin concentration in a possible ESR dosimeter: An electron spin echo study on X-irradiated ammonium tartrate

Several single crystals and powder samples of ammonium tartrate, recently proposed as a possible ESR dosimeter, have been X-irradiated with different doses. The total radical concentration has been determined by quantitative cw ESR, by comparison with a standard. The samples have been studied by electron spin echo spectroscopy. The two-pulse echo decay has been obtained and simulated by a single exponential function for different values of the microwave power of the pulses and for different pulse lengths. The dependence of the phase memory time TM on the microwave power has been exploited to get information on the contribution of the instantaneous diffusion to spin dephasing. At room temperature in the range of radical concentrations of 10(18)-10(19) spins/cm3 the instantaneous diffusion is the dominant spin dephasing mechanism. The linear dependence of the instantaneous diffusion on the total concentration of the radicals is in agreement with the theory. From the latter result we conclude that the average radical-radical distance corresponds to a random distribution of the radicals in the matrix. A simple method of measuring the radical concentration by the ESE decays in powder samples of irradiated ammonium tartrate is described.     

Spectral characterization of diffusion in porous media by the modulated gradient spin echo with CPMG sequence

Carr-Purcell-Meiboom-Gill train of radiofrequency pulses applied to spins in the constant magnetic field gradient is an efficient variant of the modulated magnetic field gradient spin echo method, which provides information about molecular diffusion in the frequency-domain instead in the time-domain as with the two-pulse gradient spin echo. The frequency range of novel technique is broad enough to sample the power spectrum of displacement fluctuation in water-saturated pulverized silica (SiO(2)) and provides comprehensive information about the molecular restricted motion as well as about the structure of medium.     

Relaxation times and line widths of isotopically-substituted nitroxides in aqueous solution at X-band

Optimization of nitroxides as probes for EPR imaging requires detailed understanding of spectral properties. Spin lattice relaxation times, spin packet line widths, nuclear hyperfine splitting, and overall lineshapes were characterized for six low molecular weight nitroxides in dilute deoxygenated aqueous solution at X-band. The nitroxides included 6-member, unsaturated 5-member, or saturated 5-member rings, most of which were isotopically labeled. The spectra are near the fast tumbling limit with T₁∼T₂ in the range of 0.50–1.1 μs at ambient temperature. Both spin–lattice relaxation T₁ and spin–spin relaxation T₂ are longer for ¹⁵N- than for ¹⁴N-nitroxides. The dominant contributions to T₁ are modulation of nitrogen hyperfine anisotropy and spin rotation. Dependence of T₁ on nitrogen nuclear spin state m_I was observed for both ¹⁴N and ¹⁵N. Unresolved hydrogen/deuterium hyperfine couplings dominate overall line widths. Lineshapes were simulated by including all nuclear hyperfine couplings and spin packet line widths that agreed with values obtained by electron spin echo. Line widths and relaxation times are predicted to be about the same at 250 MHz as at X-band.     

Multiple structure of two-pulse nuclear spin echo in cobalt films

The conditions for the formation of two-pulse echo signals from ⁵⁹Co nuclei in thin magnetic films at T=4.2 K are investigated. In the framework of the existing mechanisms, numerical simulation of the conditions for the formation of extra 3τ and 4τ echo signals (τ is the time delay between pulses) is carried out. It is shown that the multiple structure of the echo from ⁵⁹Co nuclei at T=4.2 K is due to a mechanism in which an additional hyperfine magnetic field proportional to nuclear magnetization is acting on the nuclear spin system.     

Combinatorial methods in ESR spectroscopy

Combinatorial methods based on the Pólya theory of counting and multinominal expansions are applied to the prediction of the number of hyperfine lines and their intensity patterns arising from the electronic spin and nuclear spin couplings. It is shown that these methods are very useful for predicting the ESR spectral patterns of radicals containing a large number of multinuclear spins.     

Observation of a new coherent transient in NMR -- nutational two-pulse stimulated echo in the angular distribution of \gamma-radiation from oriented nuclei

A new coherent transient in pulsed NMR, the two-pulse nutational stimulated echo, is reported for the ferromagnetic system ⁶⁰CoFe using resonant perturbations on the directional emission of anisotropic \gamma-radiation from thermally oriented nuclei. The new spin echo is a result of non-linear nuclear spin dynamics due to large Larmor inhomogeneity active during radiofrequency pulse application. It is made readily observable through the gross detuning between NMR radiofrequency excitation and gamma radiation detection, and inhomogeneity in the Rabi frequency caused by metallic skin-effect. The method of concatenation of perturbation factors in a statistical tensor formalism is quantitatively applied to successfully predict and then fit in detail the experimental time-domain data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Computational procedure to evaluate physical parameters from electron spin-echo decay functions

Analysis of the decay behavior of two-pulse and three-pulse electron spin-echo patterns gives information on the physical properties of the spin system such as the spin concentration and the spin reorientation rates. A computer-simulation approach is developed to study the effects of the spin concentration and of the spin-flip rate on the decay. The analysis is extended to two limiting models that describe different dynamic processes affecting the spectral diffusion of the spin system. The instantaneous diffusion mechanism is also taken into account. On the basis of the combined analysis of two-pulse and three-pulse simulated decay patterns the possibility of distinguishing the different dynamic models is investigated as well as the degree of accuracy in the determination of the physical quantities. A general finding is that the possibility of distinguishing the different dynamic models and the degree of accuracy depend both on the ratio between the interpulse times and the spin-flip time and on the relative weights of the spectral diffusion and instantaneous diffusion mechanisms.     

Density Matrix Simulations of the Effects of J Coupling in Spin Echo and Fast Spin Echo Imaging

A computer simulation has been used to calculate the effects of J coupling on the amplitudes of echoes produced by CPMG sequences. The program computes the evolution of the density matrix for different pulse intervals and can predict the signals obtainable from spin systems of any size and complexity. Results from the simulation confirm the prediction that a decrease in the effects of J coupling is largely responsible for the bright fat signal seen in fast spin echo imaging at high pulse rates. The effects of J coupling on CPMG echotrains are examined for A3B2 and A3B2C2 spin systems over a wide range of J coupling and chemical shift values and pulse spacings. The effects of J coupling on the point spread function obtained with fast spin echo imaging are also discussed.     

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.     

An investigation of the origins of contrast in NMR spin echo images of plant tissue.

The effects that the spatial distribution of water protons and their transverse relaxation times have on the image contrast of spin echo images of courgette was investigated. The T2-weighted image of courgette contains the most anatomical information. The image contrast was explained using a phenomenological theory based on the Bloch equations, which gave an insight into the morphology and microdynamics of water in the plant tissue. The perceived contrast in the spin echo images of courgette, glucose and Sephadex bead solutions can be dramatically altered by keeping all the imaging acquisition parameters constant, such as the recycle and echo time, but reducing the interpulse spacing by introducing a CPMG train of 180 degrees pulses into the middle of the sequence. These changes were interpreted by considering the microenvironment of the water. This work demonstrates that the origin of image contrast in T2-weighted images of plant tissue can be understood using the water proton transverse relaxation theory developed by Hills et al.     

How to measure diffusion constant and absolute susceptibility of charge carriers at the same time

Multiple spin echos can be excited for spin-1/2 systems by two radiofrequency pulses with tipping angles unequal to 180°, if the absolute magnetization is sufficiently large. If a magnetic field gradient is applied, the attenuation of the primary echo reveals the diffusion constant of these spins, whereas the ratio of primary and secondary echo amplitudes indicates the absolute magnetic susceptibility of the resonating spins. This potentiality is examined here numerically and by application of nuclear magnetic resonance to liquid samples containing protons. We analyse the complications that have to be overcome, if this technique is used for the study of the charge and spin carriers in low-symmetry quasi-one-dimensional organic conductors. Reasonable accuracy is obtained for the parameters derived for the conduction electrons of perylene radical cation salts.     

Pulsed-ESR Study of Spin Solitons as a Probe of Neutral-to-Ionic Phase Transition of TTF-CA Single Crystal

Ionic phase of charge-transfer crystal composed of tetrathiafulvalene (TTF) and p -chloranil (CA) has been studied by two-pulse electron-spin echo (ESE) at 4 K. By measuring the angular dependence of the field-swept ESE spectrum, at least three kinds of paramagnetic centers have been resolved, which are presumably ascribed to spin solitons formed at domain boundary. With varying the time separation between the microwave pulses, envelope modulations due to anisotropic hyperfine interaction have been detected. By analyzing the modulation, we have firstly obtained ENDOR spectrum of the spin solitons. Response of the ESE intensity for the optical excitation has been also examined.