Electron spin resonance and electron spin echo modulation studies of Fe-containing mesoporous MCM-48 molecular sieves

Through electron spin resonance (ESR) and electron spin echo modulation (ESEM) studies, three Fe(III) species are found in liquid ion-exchanged Fe-MCM-48 and synthesized FeMCM-48. Species A with ESR parameters g^A = 4.30 with a line width of 160 G is observed in hydrated samples. This species is accompanied by a shoulder atg = 7.60 and is assigned to distorted tetrahedral Fe(III) likely located at framework defect sites. Species B is a broad peak centered at g^B = 2.00 and is assigned to distorted octahedral Fe(III) located at extraframework sites. This species is also observed in dehydrated samples. Species C is a very narrow isotropic signal at g^C = 4.30 with a line width of 30 G and is only observed in synthesized mesophase materials. It is consistent with rhombic Fe(III) with zero field parametersD andE corresponding toD/E =1/3 and is assigned to tetrahedral Fe(III) located at framework sites. Framework Fe(III) in FeMCM-48 is less accessible to ND₃ than is extraframework Fe(III) in Fe-MCM-48. On the basis of deuterium ESEM data, framework Fe(III) in synthesized FeMCM-48 directly coordinates to two D₂O or CH₃OD molecules and interacts more weakly with two more molecules. However, no deuterium ESEM is observed for extraframework Fe(III) in ion-exchanged Fe-MCM-48 with adsorbed D₂O or CH₃OD. It is also found that Fe(III) is incorporated into the framework of FeMCM-48 at an early stage of the formation of the MCM-48 mesostructure.     

Nutation electron spin echo ofE-centers in quartz

Attenuation of the signals of the nutation echo of E’-centers in crystalline and glass quartz was experimentally investigated at room temperature. The nutation echo in EPR was excited in the single-photon regime and formed by two Zeeman-field pulses with duration t₁ and t₂ (t₁<t₂) and time interval between them τ. The echo signal was recorded during the second pulse at t≈2t₁+τ. It was established that this signal attenuation, measured as t₁ increased, follows an, exponential law, its rate Γ is much less than 1/T₂ (T₂ is the transverse relaxation time), and it linearly increases with an increase in the amplitude of the exciting SHF field B₁. The parameters of the dependence of Γ on B₁ correlate with the parameters of the analogous dependence revealed previously for attenuation of nutation of E’-centers in quartz in the two-photon regime at T=4.2 K. At the same time, the value of Γ measured with different values of τ is independent of B₁ and is equal to 1/T₁, where T₁ is the longitudinal relaxation time. A. N. Sevchenko Scientific Research Institute of Applied Physical Problems, 7, Kurchatov St., Minsk, 220064, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 405–411, May–June, 1998.     

Dynamic nuclear polarization in electron spin echo

It is shown that under the action of a proper microwave pulse sequence the equilibrium polarization of the electron spin may be transferred dynamically to the longitudinal nuclear magnetization which will oscillate due to the nuclear spin precession around the effective fields relating to differnt electron quantum number manifolds. These oscillations may be measured directly in the radiofrequency band. Analytical formulae are obtained for the case when all the nuclei coupled to an unpaired electron have spins of 1/2.     

Magnetic resonance cholangiopancreatography: comparison between respiratory-triggered turbo spin echo and breath hold single-shot turbo spin echo sequences

The purpose of this study was to compare the relative conspicuity of the pancreaticobiliary tree on respiratory-triggered three-dimensional turbo spin echo (3D TSE RT) and breath hold single-shot turbo spin echo (SSTSE BH) acquisitions respectively in MRCP imaging. Both techniques were applied to 61 patients with clinically suspected pancreaticobiliary disease using a 1.0 T MR system. All images were reviewed blindly. Qualitative comparison was made by grading subjectively the conspicuity of extrahepatic, intrahepatic, and main pancreatic ducts. Quantitative comparison included calculations of signal-to-noise ratio of the common bile duct, main pancreatic duct, gallbladder, liver, and contrast-to-noise ratio, relative contrast between common bile duct, gallbladder, and liver. 3D TSE RT provided significantly higher signal-to-noise ratio of the common bile duct (mean value 163.19) and main pancreatic duct (mean value 95.37) compared to SSTSE BH (mean values 76.24 and 26.22, respectively). 3D TSE RT was inferior to SSTSE BH for the depiction of intrahepatic ducts and pancreatic duct (head portion). 3D TSE RT and SSTSE BH sequences provide complimentary information in the visualization of the biliary and pancreatic ducts. Further comparative clinical studies are needed to redefine the sensitivity, specificity, and accuracy of MRCP using both sequences.     

Conduction electron spin resonance in magnesium

We report on the observation of conduction electron spin resonance (CESR) in samples of specially purified magnesium. Measurements were made over the temperature range 4.2–300 K and at two frequencies, 9.27 and 21 GHz. It is found that in contrast with previous data, there is no upturn in the low temperature linewidth and little variation between samples.     

Development of neutron resonance spin flipper for high resolution spin echo spectrometer

A new type of neutron resonance spin flipper (RSF) with high frequency oscillating magnetic field has been developed for Modulated IntEnsity by Zero Effort (MIEZE) spectrometer at cold neutron beam line MINE1 at JRR-3M reactor in JAEA. Dipole magnets enable us to provide the strong static fields for the RSFs. MIEZE signals have been demonstrated with the effective frequency of 600 kHz by using the new RSFs. The contrast of the signals was 0.58. The MIEZE spectrometer is under final process to practical use. The spectrometers can also be applied to the pulsed neutrons like J-PARC.     

Acoustic detection of electron spin resonance

The ESR-signal of DPPH was recorded by detecting the modulation of the absorbed microwave power with a gas-coupled microphone. This photo-acoustic detection scheme is compared with conventional ESR-detection. Applications of the acoustical detection method to other modulation spectroscopic techniques, particularly NMR, are discussed.     

Mechanisms of flexural-strain-modulated electron spin resonance

Strain-modulated electron spin resonance (SMESR) spectra of V²⁺ and Mn²⁺ centers in MgO are reported and the results are compared with those obtained for MgO : Cr³⁺. The SMESR line intensities show a characteristic angular dependence, proving that modulation of the off-diagonal elements of the $\text{G}$-tensor is the predominant mechanism when a flexural mode of vibration is applied.For V²⁺ a small additional contribution due to modulation of the diagonal elements of $\text{G}$ is present.     

Longitudinally detected electron spin resonance: Recent developments

Multiple-quantum spectroscopies are reviewed in the frame of electron paramagnetic resonance. Some properties of different nonlinear techniques are discussed for both transverse and longitudinal detection. The connections of effects recently presented with the procedure of longitudinal detection of electron paramagnetic resonance (LODESR) in presence of double transverse irradiation are stressed. Peculiarities of LODESR spectroscopy and its capabilities in facing problems related to relaxations in presence of very slow dynamic processes are evidentiated. Recent results show the vitality of the LODESR technique, that in the future could be applied to new fields, owing to experimental updating.     

Refocused primary echo: A zero dead time detection of the electron spin echo envelope modulation

We report on the two-dimensional (2D) implementation of the refocused primary electron spin echo envelope modulation (ESEEM) technique, its theory and experimental application to a model system and a system of biological interest. This technique is virtually free of dead time along one time coordinate. The ESEEM obtained by integration of the 2D time-domain data of the refocused primary ESEEM over one of the time coordinates shows the intensity of the sum combination harmonics proportional to k² for k 1 and proportional to k for k 1 (k is a usual notation for the modulation amplitude factor). This feature, in combination with the adjustment of k by means of variation of the operational frequency of the spectrometer, was found to be very useful for detection of protons with distributed hyperfine interaction parameters situated close to the electron spin.     

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.     

Nuclear spin relaxation in free radicals as revealed in a stimulated electron spin echo experiment

Electron spin echo envelope modulation (ESEEM) in a three-pulse stimulated echo experiment, when the time interval between the first and second pulses τ is varied, is attributed to a spontaneous change of the electron spin Larmor frequency in the time intervalT between the second and third pulses, due to the longitudinal relaxation of nearby nuclei. It is observed for nitroxide radicals in glassy matrices in the temperature range of 130–240 K. Nuclear relaxation is assumed to arise from fluctuation of the proton hyperfine interaction, due to fast rotation of the methyl groups. This contribution to ESEEM and the conventional one that is induced by the simultaneous excitation of allowed and forbidden electron spin transitions were found to be multiplicative. As the latter does not depend on the timeT, both contributions can be easily separated. The rate of nuclear spin relaxation was determined, and correlation time of methyl group rotation was estimated by Redfield theory of spin relaxation. Arrhenius parameters of this motion were estimated on the basis of these data and those at 77 and 90 K, where the previously developed approach was used (L.V. Kulik, I.A. Grigor’ev, E.S. Salnikov, S.A. Dzuba, Yu.D. Tsvetkov, J. Phys. Chem. A 106, 12066–12071, 2003).     

Optical detection of electron spin resonance in CdTe

We report the optical detection of electron spin resonance in p-type CdTe at 1.7 K in optical pumping conditions. The Overhauser shift of the electronic resonance, of the order of 45 G, is related to the sign of the electron g-factor g¹. We measure $\text{g}{}^1\text{= -1.59±0.02}$. Using this g¹ value and the previous results on the Knight shift, we deduce the value of the electron wavefunction on Cd in CdTe, which is consistent with the value in CdS.     

Non-linear transport in tetrathiofulvalene-tetracyanoquinodimethane: An electron spin resonance study

We describe an ESR study of pure and irradiated TTF-TCNQ in the low temperature range (1.2 K–4.2 K) where nonlinear transport has been observed. We find no evidence of an activated term in the susceptibility; our results yield an upper limit of about 10 ppm for nonmagnetic impurities with a spin-$\text{1}\text{2}$ excited state. Since in pure samples, the activated susceptibility term is not present whereas the transport nonlinearity is clearly seen, we conclude that the latter cannot be attributed to hot electron effects. The susceptibility and dc bias studies are consistent with a nonmagnetic soliton picture. We have monitored the spin resonance in the presence of a dc bias current. Using the Curie law as an internal thermometer we are able to set an upper limit on sample heating of 0.1 K at the highest dc levels used.     

Double reflection of electron spin in 2D semiconductors

The reflection of spin-polarized electrons from a potential barrier inside a quantum well (QW) is analyzed. Using Clifford (geometric) algebra it is shown that the spin–orbit interaction brings about a double reflection at an oblique incidence of an electronic beam. The reflected beam is in a superposition of two beams having different wavelengths and reflection angles which produces a two-period spatial beating pattern that can be observed experimentally in the electron spin polarization component which is normal to the QW.     

Electron spin resonance of chromia-yttria solid solutions

Electron spin resonance spectra of chromia-yttria solid solutions have been studied at room temperature for Cr concentrations between 0.20 and 2.00 mol%. Isolated Cr³⁺ ions in sites with two different symmetries were observed, as well as well as Cr³⁺ ions coupled by the exchange interaction. The relative concentration of isolated to coupled Cr³⁺ ions decreases with increasing chromium concentration. The results are consistent with the assumption that the chromium ions occupy preferentially the C₂ symmetry sites. A theoretical calculation based on this model yields an effective range of the exchange interaction between Cr³⁺ ions of 0.64 nm, of the same order as that of Cr³⁺ ions in MgO.     

sd-Exchange electron spin resonance in a ferromagnetic metal

The possibility of resonance absorption in the terahertz range caused by the sd-exchange interaction at the incidence of an electromagnetic wave on a ferromagnetic metal has been predicted. The absorption coefficient has been calculated. It has been shown that the resonance frequency is determined by the magnetization of a ferromagnet and the absorption coefficient additionally depends on the orientation of the magnetization with respect to the plane of polarization of the wave.