Molecular reorientation in pyrene hexafluoroarsenate salts

The quasi-one dimensional pyrene (PY) organic conductor (PY)₇(PY)₄(AsF₆)₄ ^. 4CH₂Cl₂shows parallel as well as 60^° rotated PY radical cations in its stacks, but crystallizes in two different modifications I and II. One of the seven intra-stack pyrene molecules is susceptible to a reorientation by 60^°, that is stable already at room temperature for modification II, but occurs at a hysteretic first order transition between 170 K and 240 K for modification I. Crystal structure, microwave conductivity and static magnetic susceptibility are typical for a quasi-one dimensional organic conductor with Peierls transition at T_P = 73 K (mod. I) or T_P = 105 K (mod. II). The pyrene radical packing is analysed by continuous wave and pulsed electron spin resonance measurements, using 9.45 GHz as well as 425 MHz as measuring frequency. Anisotropy of the conduction electron diffusion constant exceeds 1000 in the metallic phase. Received 22 March 2002 Published online 31 July 2002     

<Superscript>29</Superscript>Si nuclear spin relaxation in microcrystals of plastically deformed Si: B samples

Single crystals and microcrystals Si: B enriched with ²⁹Si isotopes have been studied using nuclear magnetic resonance and electron paramagnetic resonance (EPR) in the temperature range from 300 to 800 K. It has been found that an increase in the temperature from 300 to 500 K leads to a change in the kinetics of the relaxation of the saturated nuclear spin system. At 300 K, the relaxation kinetics corresponds to direct electron–nuclear interaction with inhomogeneously distributed paramagnetic centers introduced by the plastic deformation of the crystals. At 500 K, the spin relaxation occurs through the nuclear spin diffusion and electron–nuclear interaction with an acceptor impurity. It has been revealed that the plastic deformation affects the EPR spectra at 9 K.     

Magnetic properties of the charge ordered Nd0.75Na0.25MnO3

Nd_0.75Na_0.25MnO₃ polycrystalline ceramic is prepared via sol-gel process and its magnetic properties and electron spin resonance (ESR) spectra have been investigated experimentally. As the compound is cooled from room temperature, a charge-ordered state first develops below 170 K. A high magnetic field melts the charge ordered state and stabilizes a ferromagnetic (FM) state below 170 K. A field induced transition, analogous to a spin flip transition, is observed between 40 and 170 K. The critical temperature for spin flip increases with increasing temperature. Below 130 K, the compound tends to be intrinsically inhomogeneous, i.e. FM clusters and paramagnetic domains coexist in this system at least, which is confirmed by ESR measurements. When the external magnetic field is zero, long range FM interaction is not developed in this system; however, a tendency of re-entrant FM transition is observed in this compound.     

EPR of the first Fe(III)-containing spin-crossover metallomesogens

The low-spin (LS) to high-spin (HS) transition in two mesogenic Fe(III) complexes with alkyloxysalicyliden-N^′-ethyl-N-ethylendiamine as ligands is studied by electron paramagnetic resonance (EPR). The symmetrization of the crystal field around the Fe(III) ion under first heating of a polycrystalline sample from the room temperature was observed in the spectra of HS complexes. The line narrowing (from 45 to 15 mT) under the crystal-smectic phase transition is explained by the strengthening of the intermolecular exchange interaction, as a result of the structural reorganization of layers in the smectic phase. A feature of both mesogenic spin-transition systemsis an unusual field-induced spin instability which leads to the hysteresis of the HS-LS composition. This instability is detected by EPR and magnetic susceptibility methods. The alignment of systems by magnetic field in the mesophase and a complete or partial orientational order under cooling the mesophase to the glass state are the main reason for this hysteresis. The influence of EPR-silent LS complexes reveals itself in the line broadening of HS compounds’ when the temperature is lowered from 220 K.     

Electron paramagnetic resonance study of the nuclear spin dynamics in an AlAs quantum well

The nuclear spin dynamics in an asymmetrically doped 16-nm AlAs quantum well grown along the [001] direction has been studied experimentally using the time decay of the Overhauser shift of paramagnetic resonance of conduction electrons. The nonzero spin polarization of nuclei causing the initial observed Overhauser shift is due the relaxation of the nonequilibrium spin polarization of electrons into the nuclear subsystem near electron paramagnetic resonance owing to the hyperfine interaction. The measured relaxation time of nuclear spins near the unity filling factor is (530 ± 30) min at the temperature T = 0.5 K. This value exceeds the characteristic spin relaxation times of nuclei in GaAs/AlGaAs heterostructures by more than an order of magnitude. This fact indicates the decrease in the strength of the hyperfine interaction in the AlAs quantum well in comparison with GaAs/AlGaAs heterostructures.     

Quenching spin decoherence in diamond through spin bath polarization

We experimentally demonstrate that the decoherence of a spin by a spin bath can be completely eliminated by fully polarizing the spin bath. We use electron paramagnetic resonance at 240 GHz and 8 T to study the electron-spin coherence time T2 of nitrogen-vacancy centers and nitrogen impurities in diamond from room temperature down to 1.3 K. A sharp increase of T2 is observed below the Zeeman energy (11.5 K). The data are well described by a suppression of the flip-flop induced spin bath fluctuations due to thermal electron-spin polarization. T2 saturates at approximately 250 micros below 2 K, where the polarization of the electron-spin bath exceeds 99%.     

Magnetic phase separation in europium hexaboride and its relation to the Kondo interaction

Europium hexaboride single crystals have been investigated using the electron paramagnetic resonance at a frequency of 9.25 GHz in the temperature range 10–300 K. The magnetic phase separation of the spin system of europium ions Eu²⁺ is observed. The cause of the separation is the formation of the polarons of two types associated with the Kondo and anti-Kondo couplings of charge carriers of the valence and conduction bands, respectively, with the localized magnetic moments of Eu²⁺.     

基于电子顺磁共振的ZnTPP激发态及其TEMPO各向异性的研究

为了研究卟啉类敏化剂的光致激发态能量转移和电子转移问题,本文基于紫外可见光谱仪和电子顺磁共振波谱仪,构建了以锌卟啉为研究对象的"锌卟啉-稳态自由基-二甲苯"实验体系.锌卟啉的紫外可见光谱显示,在可见光谱的B带和Q带出现明显的特征峰,是锌卟啉分子中电子由基态能级跃迁至激发态能级产生的.低温条件下受紫外可见光辐照的实验体系的电子顺磁共振波谱,检测到了稳态自由基四甲基哌啶氧化物的增强吸收电子顺磁共振波谱.根据分子激发态相关理论、光化学物理反应理论和化学诱导电子自旋极化理论对实验结果进行了分析,结果表明,四甲基哌啶氧化物稳态自由基电子顺磁共振波谱的增强吸收对应于锌卟啉光致激发态的能量转移和电子转移;四甲基哌啶氧化物在低温(143 K)下的电子顺磁共振波谱表现出的各向异性特征现象来源于氮氧自由基电子与氮核的各向异性超精细相互作用.     

Magnetic resonance study of Ce and Gd doped NiFe2O4 nanoparticles

Present work is a study of temperature dependent electron paramagnetic resonance spectra of Ce and Gd doped nickel ferrite nanoparticles. The samples, synthesised by chemical route were characterised by X-ray diffractometer, electron paramagnetic resonance spectroscopy (EPR) and vibrating sample magnetometer (VSM). The average crystallite size of pure nickel ferrite is ∼64 nm and for Gd and Ce doped samples it is ∼20 nm and ∼14 nm, respectively. The EPR spectra were recorded from 120 to 300 K. Doping with Gd and Ce reduces the line width and g-value in comparison to that of pure nickel ferrite. Ce doped samples have the lowest values of both these parameters at room temperature. This indicates that Ce doped samples show lowest loss and is suitable for high frequency devices. EPR spin numbers are reduced while the spin relaxation time is increased after doping with rare earth ions. Gd doped samples have higher values of relaxation time and lower spin numbers in comparison to that of Ce doped samples. VSM results show that the magnetisation and coercivity are reduced after doping with both Ce and Gd rare earth ions.     

13C spin-lattice relaxation in natural diamond: Zeeman relaxation at 4.7 T and 300 K due to fixed paramagnetic nitrogen defects

13C spin-lattice relaxation times in the laboratory frame, ranging from 1.4 to 36 h, have been measured on a suite of five natural type Ia and Ib diamonds at 4.7 T and 300 K. Each of the diamonds contains two types of fixed paramagnetic centers with overlapping inhomogeneous electron paramagnetic resonance (EPR) lines. EPR techniques have been employed to identify these defects and to determine their concentrations and relaxation times at X-band. Spin-lattice relaxation behavior of 13C in diamonds containing paramagnetic P1, P2, N2. and N3 centers are discussed. Depending on the paramagnetic impurity types and concentrations present in each diamond, three different nuclear spin-lattice relaxation (SLR) paths exist, namely that due to electron SLR mechanisms and two types of three-spin processes (TSPs). The one three-spin process (TSP1) involves a simultaneous transition of two electron spins belonging to the same hyperfine EPR line and a flip of a 13C spin, while the other process (TSP2) involves two electron spins belonging to different hyperfine EPR lines and a 13C spin. It is shown that the thermal contact between the 13C nuclear Zeeman and electron dipole-dipole interaction reservoirs is field dependent, thus forming a bottleneck in the 13C relaxation path due to TSP1 at high magnetic fields.     

Defects in thin film silicon at the transition from amorphous to microcrystalline structure

Defects in thin film silicon with different structure all the way from amorphous to microcrystalline were investigated by electron spin resonance with emphasis on amorphous material prepared close to the transition to crystalline growth. Electron beam irradiation and stepwise annealing is used for reversible variation of the defect density over three orders of magnitude. The electron irradiation enhances mainly the native paramagnetic defects. Additional resonances are found as satellites to the central line, which anneal rapidly at temperatures below 100 °C. These features are most pronounced for the amorphous material prepared close to the transition to crystalline growth. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The dynamical transition in proteins of bacterial photosynthetic reaction centers observed by echo-detected EPR of specific spin labels

An echo-detected electron paramagnetic resonance (ED EPR) approach was used to study molecular dynamics in photosynthetic reaction centers (RCs) fromRhodobacter sphaeroides R26, employing the specific spin label methanethiosulfonate and 3-maliemido proxyl. ED EPR has recently been shown to be sensitive to so-called dynamical transition in disordered media, which is characterized by the transition from a harmonic-like librational motion of a molecule to an anharmonic one or to a stochastic wobbling motion. ED EPR line shapes studied over a wide temperature range reveal a sharp transition occurring above 180 K. The possible relation of the found transition to the temperature dependence of electron transfer reactions in RC is discussed.     

EPR spectra of Fe centers in layered TlGaSe2 single crystal

A single-crystal TlGaSe₂ doped by paramagnetic Fe ions has been studied at room temperature by electron paramagnetic resonance (EPR) technique. The fine structure of EPR spectra of paramagnetic Fe³⁺ ions was observed. The spectra were interpreted to correspond to the transitions among spin multiplet (S=5/2, L=0) of Fe³⁺ ion, which are splitted by the local ligand crystal field (CF) of orthorhombic symmetry. Four equivalent Fe³⁺ centers have been observed in the EPR spectra and the local symmetry of crystal field at the Fe³⁺ site and CF parameters were determined. Experimental results indicate that the Fe ions substitute Ga at the center of GaSe₄ tetrahedrons, and the rhombic distortion of the CF is caused by the Tl ions located in the trigonal cavities between the tetrahedral complexes.     

ESR investigation of Cr diffusion in MgO powders

The electron spin resonance (ESR) technique was used to investigate the diffusion of Cr³⁺ in magnesium oxide (MgO) powders. The ESR absorption intensity was measured for several annealing times and four different temperatures of isothermal annealing: 1223, 1273, 1323 and 1373 K. The activation temperature for diffusion, calculated from the experimental data using a theoretical model based on the Fick equation, was found to be E_A=212±9 kJ mol⁻¹. This result is about 30% smaller than similar data obtained for single-crystal MgO using the radioactive-tracer sectioning technique. The difference is attributed to a higher concentration of defects in the powder relative to single crystals.     

Influence of zeolite water on paramagnetic and ferromagnetic resonances in the Co2[Nb(CN)8] · 8H2O molecular magnet

The contributions of Co²⁺ and Nb⁴⁺ ions to the high-frequency dynamic magnetic susceptibility of the Co₂[Nb(CN)₈] · 8H₂O molecular magnet in the paramagnetic state at T > 12 K are separated. It is found that the ferromagnetic ordering, which leads to the reconstruction of the electron paramagnetic resonance spectrum into the ferromagnetic resonance spectrum, occurs at T < 12 K. The influence of zeolite water on the spectra of the paramagnetic and ferromagnetic resonances is found. Dehydration leads to a decrease in the time of the spin relaxation of the ferromagnetic system from 50 ps to 17 ps at T = 4 K and to the variation in the temperature dependences of the widths of the lines and g factors in the electron spin resonance spectra.     

Detection of interstitial Ga in GaN

We report the direct detection of interstitial Ga by optical detection of electron paramagnetic resonance (ODEPR) in the photoluminescence of n-type GaN after irradiation in situ at 4.2 K with 2.5 MeV electrons. It is stable upon annealing until room temperature, where it becomes mobile and trapped to form a new defect which is observed to emerge as the interstitial disappears. The time constant of the process at room temperature is approximately 200 min. The emergence of another ODEPR center beginning at approximately 135 K suggests even easier migration of one of the other intrinsic defects in the GaN lattice.     

EPR Features of Spin-Crossover in Tris(<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dialkyl-Dithiocarbamato)Iron(III)

The temperature dependence of electron paramagnetic resonance (EPR) spectra of a series of dithiocarbamates Fe(RR′dtc)₃ was studied in the temperature range from 5 to 300 K. A small part of solvated complexes serving as spin probes in the EPR-silent matrix enabled the observation of EPR of the Fe(III) ion in the whole temperature range. The spin transition was revealed in the reduction of the integral intensity of the signal from the high-spin complexes and in the non-monotonous change of the line width with temperature decrease due to the effect of the low-spin complexes with short spin–lattice relaxation times. Below ca. 60 K, the ferromagnetic ordering of the magnetic moments in low-spin particles (“domains”) arising at the spin transition was observed.     

Electron paramagnetic resonance in YbNiAl<Subscript>2</Subscript> single crystals with strong magnetic anisotropy

Anisotropy in the magnetic properties of YbNiAl₂ intermetallide has been studied. Electron paramagnetic resonance (EPR) signals assigned to the localized magnetic moments of trivalent ytterbium have been detected at temperatures below 20 K. Spin–lattice relaxation processes like the Orbach–Aminov process with participation of the first excited Stark sublevel of the Yb³⁺ ion with an energy of 96 K govern electron–spin dynamics and the disappearance of spectrum lines with a further increase in temperature. Strong magnetic anisotropy effects are discussed as a main reason for the appearance of electron paramagnetic resonance.     

Lattice distortion (Peierls Transition) caused by spin interaction in the chaotic impurity system of a semiconductor

The effect of an elastic spontaneous distortion of the crystal lattice of a doped semiconductor Ge:As near the insulator–metal (IM) phase transition has been discovered. The effect is manifested in the electron spin resonance (ESR) of neutral As atoms as a splitting of the single resonance absorption line. It observed at electron concentrations in the range 0.8 < n/n_C < 1 at low temperatures T < 100 K (n_C = 3.7 × 10¹⁷ cm^‐3 is the critical electron concentration for the IM phase transition). The splitting is the strongest along each of the six [110] directions, which indicates that the local lattice distortion occurs just in these directions. As a result, a sample is possibly divided into separate domains differing in the directions of compressive or tensile deformations. A study of concentration, temperature, and angular dependences of the effect has shown that the phenomenon discovered can be understood in terms of the Peierls spin transition model.     

Correlation between the negative magnetoresistance effect and magnon excitations in single-crystalline CuCr1.6V0.4Se4

Structural, electrical and magnetic measurements, as well as electron spin resonance (ESR) spectra, were used to characterise the single-crystalline CuCr_1.6V_0.4Se₄ spinel and study the correlation between the negative magnetoresistance effect and magnon excitations. We established the ferromagnetic order below the Curie temperature T _C ≈ 193 K, a p-type semiconducting behaviour, the ESR change from paramagnetic to ferromagnetic resonance at T _C, a large ESR linewidth value and its temperature dependence in the paramagnetic region. Electrical studies revealed negative magnetoresistance, which can be enhanced with increasing magnetic field and decreasing temperature, while a detailed thermopower analysis showed magnon excitations at low temperatures. Spin–phonon coupling is explained within the framework of a complex model of paramagnetic relaxation processes as a several-stage relaxation process in which the V³⁺ ions, the exchange subsystem and conduction electron subsystem act as the intermediate reservoirs.