ESR, ENDOR, and ESEEM investigations on UV-irradiated 2,4,6-tri-tert-butyl phenol crystals

Electron spin resonance (ESR), electron nuclear double resonance (ENDOR), and electron spin echo envelope modulation (ESEEM) measurements were carried out for UV-irradiated 2,4,6-tri-tert-butyl phenol in the polycrystalline state. The radical produced in the crystal was detected by ESR and identified to be the corresponding phenoxyl radical, which is well characterized in the chemical oxidations in solutions. ENDOR and ESEEM spectra were unambiguously analyzed in terms of the hyperfine coupling constants determined from well-resolved ESR in solutions. Radical pairs in the crystals were also ascertained, and together with the single-crystal study the analysis disclosed zero-field splitting parameters in the triplet states. ESEEM time decays gave relaxation timesT ₁ = 5.94 andT ₂ = 1.12 μs at room temperature. These appropriate values permit an easy detection of the spin echoes, and therefore this radical matrix can be used as a useful standard for pulsed ESR investigations.     

氢化非晶锗碳薄膜中的自旋缺陷态

本文应用原位电子自旋共振(ESR)技术研究了射频反应溅射法制备的氢化非晶锗碳(a-Ge_1-xC_x:H)薄膜中自旋缺陷态的种类、密度、温度依赖关系和热力学动态行为。在分解ESR谱的过程中,发现了它的不对称成分,并对此进行了定量分析和微观机理的探讨。 关键词：     

X-Band ESR and51V NMR study of the Haldane system PbNi2−xMgxV2O8

The temperature and angular dependence of the X-band electron spin resonance (ESR) and⁵¹V nuclear magnetic resonance (NMR) spectra have been measured in a recently discovered Haldenegap system, PbNi_2-xMg_xV₂O₈ (0≤x≤0.24). The angular dependence of the ESR signal suggests that both the spin diffusion as well as the magnetic anisotropy determine the electronic spin correlation functions. However, in doped samples the magnetic anisotropy increasingly dominates the spin dynamics on cooling. The huge broadening of the⁵¹V NMR spectra in doped samples at low temperatures provides evidence for localized magnetic moments in the vicinity of the Mg impurities. Locally distorted structure around each Mg impurity may slightly modify the magnetic interactions and be potentially responsible for the antiferromagnetic ordering (belowT _N≈ 3.5K) in doped compositions.     

Photoinduced C70 radical anions in polymer:fullerene blends

Photoinduced polarons in solid films of polymer:fullerene blends were studied by photoluminescence (PL), photoinduced absorption (PIA) and electron spin resonance (ESR). The donor materials used were P3HT and MEH‐PPV. As acceptors we employed PC₆₀BM as reference and various soluble C₇₀‐derivates: PC₇₀BM, two different diphenylmethano‐[70]fullerene oligoether (C₇₀‐DPM‐OE) and two dimers, C₇₀–C₇₀ and C₆₀–C₇₀. Blend films containing C₇₀ revealed characteristic spectroscopic signatures not seen with C₆₀. Light‐induced ESR showed signals at g ≥ 2.005, assigned to an electron localized on the C₇₀ cage. The formation of C₇₀ radical anions also leads to a subgap PIA band at 0.92 eV, hidden in the spectra of C₇₀‐based P3HT and MEH‐PPV blends, which allows for more exact studies of charge separated states in conjugated polymer:C₇₀ blends. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Composition,temperature and radiation induced changes in gamma irradiated AAAMPS copolymer

Effect of composition, temperature and radiation dose in gamma irradiated acrylamide-2-acrylamido-2-methyl propane sulphonic acid (AA) copolymer has been investigated by electron spin resonance (ESR) and fourier transform infrared (FTIR) techniques. ESR spectra of gamma irradiated AA copolymer have been recorded under different conditions. The observed ESR spectra are analysed by computer simulation techniques, to separate the constituent component spectra. Magnetic parameters employed to simulate the component spectra enabled the identification of corresponding free radicals. The AA copolymer with low acrylamide content composed of macroradicals of the type ?CH₂?CH?CH₂? and methyl radicals (CH₃) whereas the copolymer with high acryl amide content possess methyl radicals and radicals of the type ?CH₂?C(CONH₂)?CH₂?/CH₃?C?CH₃. Reasons for the variation in the formation of free radicals have been explained. The observed changes in ESR spectra of irradiated AA copolymer at higher temperatures are thought to be due to the recombination of free radicals. Formation of free radicals found to be enhanced with the increase in dose of irradiation. FTIR spectra of pure and irradiated copolymers have also confirmed the previous results.     

Effect of radiation dose with low dose rate on degradation of propylene–ethylene copolymer

Medical grade propylene–ethylene (P–E) copolymer was irradiated by gamma rays. The radicals generated in the irradiated P–E copolymer were identified by using electron spin resonance (ESR) technique and the structural changes in the polymer were monitored with Fourier transform infrared spectroscopy (FTIR). The ESR spectra were analysed with computer simulations. The ESR studies show the formation of macro (～CH₂–?H–CH₂～), peroxy (POO˙), methyl and acyl (R–?=O) radicals and the asymmetric doublet, characteristic of peroxy radicals in the case of the sample irradiated at low dose (1 Mrad) and high doses (30 and 40 Mrad), respectively. The FTIR spectra of irradiated P–E copolymer indicate an increase in the concentration of peroxide groups. The absorption bands of –C=O and –OH groups were increased and the decline in the intensity of –CH₃ group absorption band is reported.     

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.     

Polaron motional narrowing of electron spin resonance in organic field-effect transistors

Polaron states in organic thin-film transistors (TFTs) were investigated by the electron spin resonance (ESR) technique. Gate-field-dependent and temperature-dependent single-Lorentzian ESR spectra were observed for field-induced polarons in pentacene TFTs, demonstrating the effect of motional narrowing due to polaron diffusion. Analyses of the ESR linewidth revealed a considerably long trapping time (tau_(C) approximately 0.7 ns), the variation of which is discussed in terms of the multiple trap-and-release model.     

Spin solitons and waves in chiral molecular ferrimagnets

Resonance modes corresponding to a spin-soliton resonance have been found in the electron spin resonance spectra of [Cr(CN)₆][Mn(S)-pnH-(H₂O)]H₂O two-dimensional (2D) chiral single crystals and [Mn{(R/S)-pn}]₂[Mn{(R/S)-pn}₂(H₂O)][Cr(CN)₆]₂ chiral single crystals with a 3D magnetic order. It is also established that the chiral crystals of both types exhibit a spin-wave resonance analogous to the excitation of standing spin waves in thin magnetic films. At the same time, racemic crystals of the first type do not exhibit spin-soliton resonance. The entire body of experimental data indicates that the chirality of crystals influences the spin excitations (standing spin waves and solitons) in these media.     

Magnetic relaxation in UCu4 + xAl8 - x

A quasielastic neutron scattering study has been performed on UCu_4+xAl_8-x, a system which reveals an alloying-induced transition from magnetic order to heavy-fermion behavior. The magnetic response can be described by a broad quasielastic Lorentzian for all concentrations. No crystal field excitations could be detected. Remarkably, the linewidth decreases with increasing hybridization strength and seems to be no measure of the Kondo lattice temperature T*. In addition, electron spin resonance (ESR) experiments were performed which revealed that, even in the heavy-fermion regime, spin fluctuations play an important role. Both experimental findings are in distinct contrast to cerium-based heavy fermion systems.     

Electron spin resonance in manganese-doped BSCCO (2212) crystals

The electron spin resonance (ESR) spectra of undoped and manganese-doped BSCCO (2212) crystals (nominal composition Bi₂Sr₂CaCu_2–x Mn_xO_y, where x=0.1) are compared. Zh. Tekh. Fiz. 67, 137–138 (October 1997)     

ESR and endor studies of the VK center in SrF2

The results of electron spin resonance (ESR) and electron nuclear double resonance (ENDOR) studies of a self-trapped hole (V_K center) in SrF₂ are reported. The g-factor and hyperfine interaction constants were determined for the flourine nuclei forming the center and for those in the nearest three different sites. The values of hyperfine interaction constants are intermediate to the known values for CaF₂ and BaF₂.     

Mössbauer effect and electron spin resonance study of CdxMg1−xFe2O4 system

This work deals with the application of Mossbauer Effect (ME) in studying the crystal electric field and the cation distribution among tetrahedral (A) and the octahedral (B) sites of the spinal structure in the ferrite system Cd_x Mg_1–x Fe₂O₄ (x=0, 0.2,...1). The electron spin resonance technique (ESR) was also applied for studying this ferrite system. It was possible to characterize the ESR spectra of ferrite through the combination with the ME spectra.The ESR spectra of magnesium ferrite showed two resonance positions of Fe³⁺ ions and indicated that a strong exchange interaction is dominant in the pure Mg-ferrite. For high Cd concentration ferrites only single resonance line was observed. These results could be interpretted on the basis of the ME results where it indicated that Cd²⁺ ions prefer tetrahedral positions, forcing the Fe³⁺ ions from these positions to join those in the octahedral sites. The complete site occupation with different types of cations was successfully achieved from the ME spectra. The values of the quadrupole splitting indicated that for each ferrite in the system there exists an electric field gradient surrounding the Fe³⁺ ions in each of the octahedral and tetrahedral sites. The increase in the Mg-concentration increases the symmetry of the electric field at these sites.     

Electron spin resonance study of the dynamic magnetic susceptibility of CuO, Cu1−x Zn x O, and Cu1−x Li x O single crystals

Results are presented of studies of the dynamic magnetic susceptibility of CuO, Cu_1?x Zn _x O (x ≈ 1.5%), and Cu_1?x Li _x O (x ≈ 1%) single crystals. The orientational dependence of the ESR spectra was investigated at room temperature. The results for CuO are analyzed using a model of a quasi-one-dimensional antiferromagnet (S = 1/2) with anisotropic exchange interaction between Cu²⁺ spins in the chains and exchange coupling between the chains allowing for one-dimensional spin diffusion and spinon excitations. The estimated line width is of the same order of magnitude as the experimental data. Substituting Cu with Zn scarcely alters the spin dynamics of the Cu²⁺ ions, as in weakly diluted magnets. Lithium doping substantially increases the ESR line width and this is attributed to excess holes forming rapidly relaxing spin complexes with copper ions.     

La0.3Ca0.7Mn1－xVxO3体系的有序相和再入型自旋玻璃行为研究

通过对La_0.3Ca_0.7Mn_1－xV_xO₃(x=0.05,0.10,0.134,0.20)体系的M-T曲线、ρ-T曲线、ESR谱的测量,研究了Mn位掺V对La_0.3Ca_0.7MnO₃体系电荷序和自旋序的影响.结果表明,当0.05≤x≤0.134时, 体系存在电荷有序(CO)相,其自旋序随温度降低发生顺磁(PM)-电荷有序(CO)-反铁磁(AFM)变化.当x＝0.20时,CO相逐步融化,在40 K发生自旋玻璃转变,表现出再入型的自旋玻璃行为,低温下的基态存在着多种复杂的磁相互作用之间的竞争机理. 关键词： 电荷有序 自旋序 相分离 再入型自旋玻璃行为     

Electron spin resonance determination of proton locations in a hydride

The low temperature electron spin resonance (ESR) spectrum of dilute Er in ScH_x powder contains distinct signals which are due to the presence of octahedral as well as tetrahedral protons in the vicinity of the Er ions. The occupation probability for the octahedral protons versus the bulk hydrogen-to-metal ratio is determined from the ESR signal intensities and compared with a lattice-gas calculation.     

Gd3+ electron spin resonance spectroscopy on LaO1 ? x F x FeAs superconductors

We report an electron spin resonance (ESR) spectroscopy study on polycrystalline samples of the LaO_{1 ? x} F _x FeAs (x = 0 and 0.1) compound with small levels of Gd doping (2% and 5%). The Gd ESR signal is found to be sensitive to the magnetic phase transition from the paramagnetic to the spin density wave (SDW) state occurring in the parent LaO_{1 ? x} F _x FeAs compounds at T _SDW ?? 130 K. Interestingly, the analysis of the low-temperature ESR spectra of the c-axis oriented Gd_{1 ? y} La _y OFeAs samples gives evidence for the magnetically nonequivalent Gd sites and also for sites having a different local charge environment. The analysis of the temperature dependence of the ESR linewidths gives evidence for a coupling of the localized 4f electrons of Gd to the conduction electrons in the FeAs layers. The ESR data reveal that the fluorine substitution, which provides electron doping, suppresses the SDW order and enhances the density of states in the electronic bands stemming from the xz and yz orbital states of Fe to which the 4f electrons are most strongly coupled.     

The possibility of observing a soliton mode in [(CH3)4N] [NiCl3] by neutron scattering experiments

The contribution of solitons, existing as bound states of spin excitations and lattice oscillation, to the dynamic structure factor in ferromagnetic chains of [(CH₃)₄N] [NiCl₃] is evaluated. At sufficiently low temperatures these low-energy soliton excitations determine the thermodynamic properties of the system and can be revealed by observing the quasielastic component in the neutron scattering spectrum.     

Electron spin resonance study of Fe doping effect in La0.67Ca0.33MnO3

Electron spin resonance (ESR) study was carried out on La_0.67Ca_0.33Mn_1−xFe_xO₃ (x=0.0, 0.04) samples. The temperature dependence of the ESR spectra indicates the presence of phase separation above and below T_C in x=0.0 and 0.04 sample, respectively. The increase of the g-value in the high-temperature region indicates the existence of local spin correlations even in the paramagnetic state. The activation energy obtained from both the temperature dependence of the ESR intensity and linewidth exhibits a smaller value in the Fe-doped sample. Our study suggests that the ferromagnetic spin correlations would be significantly weakened by a slight doping of Fe ions on Mn sites.     

Etude par resonance paramagnetique electronique de sulfures de molybdene et de tungstene

Chalcogenides MeS_3−x (Me = Mo, W; 0 ⩽ x ⩽ 1) have been prepared by the thermal decomposition of tetrathiometallates. These compounds are largely amorphous; desulfurization as well as crystalline organization occur when the heat treatment temperature (TT) increases. At 1000°C a perfect hexagonal arrangement can be obtained (x = 1). ESR spectra of amorphous species having x in the range 0–1 have been recorded. A part of the ESR signals is ascribed to sulfur chains whilst the other part is attributed to Me (V) species. The intensity of both series of ESR lines is a decreasing function of TT. The spectra are characteristic of Me (V) in an axial symmetry environment. At TT ≅ 1000°C a narrow ESR signal remains, which is assigned to electron spin centers of impurities (g-value close to that of the free electron). The results are explained either in terms of continuous structural evolution of the solid during heat treatment or in terms of a biphasic mixture of amorphous MoS₃ and MoS₂. The variation of the spin concentration as a function of TT is reported and compared with the results previously obtained from a study of the transport properties of these solids. In all cases the values obtained for Me = W are smaller than those observed on Me = Mo.