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1.
By employing the perturbation formulae of the spin Hamiltonian parameters (SHPs) (g factors gxx, gyy, gzz, hyperfine structure constants Axx, Ayy, Azz and superhyperfine parameters Axx׳, Ayy׳, Azz׳) for a 3d1 ion in orthorhombically elongated octahedra and tetrahedra, the defect structures and the experimental EPR spectra are theoretically and systematically investigated for the two orthorhombic Ti3+ centers C1 and C2 in ZnWO4. Center C1 is ascribed to the impurity Ti3+ at host W6+ site associated with two nearest neighbor oxygen vacancies due to charge compensation. The resultant tetrahedral [TiO4]5– cluster is determined to undergo the local orthorhombic elongation distortion, characterized by the axial distortion angle Δθ (=θ–θ0≈–6.84°) of the local impurity-ligand bond angle θ related to θ0 (≈54.74°) and the perpendicular distortion angle Δε (=ε–ε0≈2.5°) related to ε0 (≈45°) of an ideal tetrahedron because of the Jahn–Teller effect. Center C2 is attributed to Ti3+ on Zn2+ site, and this octahedral [TiO6]9– cluster may experience the local axial elongation ΔZ (≈0.001 Ǻ) and the planar bond angle variation Δφ (≈9.1°) due to the Jahn–Teller effect, resulting in a more regular oxygen octahedron. All the calculated SHPs (i.e., g factors for both centers, the hyperfine structure constants for center C2 and superhyperfine parameters of next nearest neighbor ligand W for center C1) show good agreement with the observed values. However, the theoretical results based on the previous assignment of center C1 as Ti3+ on W6+ site with only one nearest planar oxygen vacancy (i.e., five-fold coordinated octahedral [TiO5]7– cluster) show much worse agreement with the experimental data. The defect structures and the SHPs (especially the g anisotropies) are discussed for both centers. The present studies on the superhyperfine parameters of ligand W6+ for center C1 would be helpful to further investigations on the superhyperfine interactions of cation ligands which were rather scarcely treated before. 相似文献
2.
Electron spin resonance spectra of Mn2+ in diluted solid solutions of MnO2 in Y2O3 have been studied at room temperature for Mn concentrations between 0.20 and 2.00 mol%. Isolated Mn2+ ions in sites with two different symmetries were observed, as well as Mn2+ ions coupled by the exchange interaction. The relative concentration of isolated to coupled Mn2+ ions decreases with increasing manganese concentration. The results are consistent with the assumption that the manganese ions occupy preferentially the C2 symmetry sites. A theoretical calculation based on this model yields an effective range of the exchange interaction between Mn2+ ions of 0.53 nm, of the same order as that of Mn2+ ions in CaO. 相似文献
3.
A Garcia-Quiroz David L AzevedoE.C da Silva 《Journal of Physics and Chemistry of Solids》2002,63(10):1863-1866
Properties of oxygenated carbon nitride films have attracted the attention of physics researchers due to their magnetic and physical properties, as well as for their usefulness in the industry. The free radicals were investigated using electron paramagnetic resonance applied in the study of spin concentration due to the different mechanism of preparation of carbon nitride films by RF-discharge with different kinds of plasma. Unpaired spin concentrations, in the order of 1020 per cm3, were measured and their time recombination dependency was important in those films. The films were grown by plasma enhanced chemical vapor deposition using mixtures of hydrocarbons, N2 and O2 in different proportions. 相似文献
4.
Electron paramagnetic resonance (EPR) investigations has been carried out on the new family of molybdenum doped vanadium sesquioxides (V1−xMox)2−δO3. The oxidation effects were monitored from the rate of paramagnetic V4+ created when the sample is exposed to the air. The effects of the oxidation time, sample temperature, and annealing at 1000 °C under a diluted hydrogen atmosphere on the EPR signal features are analyzed. The V4+ concentration in the oxidized samples is determined and the relaxation effects driven by the conduction electrons are pointed out from the thermal behaviour of the EPR line features. EPR spectra of all the oxidized samples also reveal a small ferromagnetic contribution strongly correlated with the V4+ content. 相似文献
5.
Cr-doped mullites were prepared from single-phase precursors containing up to 9.60 wt% Cr2O3 using a sol-gel technique followed by thermal treatment. Particle induced X-ray emission spectroscopy and X-ray powder diffraction were used to characterize the samples. Mullites were orthorhombic, space group Pbam. Cr doping caused the increase of unit-cell parameters. Strongest expansion was noticed along c-axis followed by a and b (Δc/c=0.089, Δa/a=0.061, Δb/b=0.045% per mole Cr2O3). A second phase, namely θ-(Al,Cr)2O3, was revealed by XRD in the sample containing 9.60 wt% Cr2O3. The structure of mullites was refined by the Rietveld method, location of Cr3+ was performed by the EPR spectroscopy. At low chromium doping level (Cr2O3 content less than ∼5 wt%) Cr3+ ions were substituted for Al3+ in the AlO6 octahedra of the mullite structure (M1 site). For higher doping level, Cr3+ ions were additionally substituted for Al3+ in the AlO6 octahedra of the second phase [θ-(Al,Cr)2O3 at 1400 °C, or α-(Al,Cr)2O3 at 1600 °C] which segregated in the system. Substitution of Cr3+ for Al3+ on M1 site in the mullite structure resulted in increase of average distances in (M1)O6 octahedron and decrease of average distances in T*O4 tetrahedron, while average distances in TO4 tetrahedron stayed almost constant. 相似文献
6.
P. Pellegrino B. Garrido C. García R. Ferr J. A. Moreno J. R. Morante 《Physica E: Low-dimensional Systems and Nanostructures》2003,16(3-4):424
The ability of surface passivation to enhance the photoluminescence (PL) emission of Si nanocrystals in SiO2 has been investigated. Silicon precipitation in implanted samples takes place in a time scale of few minutes at 1100°C. For longer annealing at the same temperature, the PL intensity of the Si nanocrystals increases and eventually reaches saturation, while it correlates inversely with the amount of Si dangling bonds at the Si–SiO2 interface (Pb centers), as measured by electron spin resonance. This combined behavior is independent on the silica matrix properties, implantation profiles and annealing atmosphere and duration. The observation that the light emission enhancement is directly related to the annealing of Pb centers is confirmed by treatment in forming gas. This mild hydrogenation at much lower temperature (450°C) leads to a complete passivation of the Pb defects, increasing at the same time the PL yield and the lifetime. 相似文献
7.
研究了阿富汗青金石矿石、敦煌石窟青金石颜料、合成群青的呈色机理。实验表明三者均有g=2.029峰,前两者多一个g=2.047峰,400℃时,g=2.047峰变平,600℃时消失。g=2.029峰随温度升高而增强,800℃时增强放慢,颜色也随温度变深。在M0O3/SiO2和M0O3/Al2O3表面上,S2^-的EPR有g1=2.047,g2=2.208,g3=1.998三个分量。因此,群青、青金石和 相似文献
8.
对电子自旋1/2≤S<3.5,核自旋1/2≤I<4.5和配体少于10个的顺磁体系的多晶EPR谱的拟合进行研究。在VAX-11/785计算机上用FORTRAN语言建立EPR谱模拟程序包,计算了多个例子,获得较为满意的结果。 相似文献
9.
The molecular orientation distribution function of a stable radical 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl in magnetic-field oriented 4-cyano-4’-n-pentylbiphenyl was determined from the angular dependence of the ESR spectra. The preferred molecular orientation of radical species in the liquid crystal matrix was determined. The temperature evolution of the orientation distribution function was studied.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 190–195, January, 2005. 相似文献
10.
Complex systems of paramagnetic centres existing in demineralised flame coal (71.4 wt% C), medium-rank coal (85.6 wt% C) and
anthracite (94.9 wt% C) were analysed by electron paramagnetic resonance spectroscopy (EPR). Different groups of paramagnetic
centres were searched in macerals (exinite, vitrinite, inertinite) of coals with carbon contents of 73.8 wt% C and 85.6 wt%
C. Experimental EPR spectra were fitted by different superposition of theoretical lines. Total concentration of paramagnetic
centres both in coal and macerals increases with carbon content in the sample. Total concentration of paramagnetic centres
in macerals increases from exinite to inertinite. Four groups of paramagnetic centres were found in medium-rank coal, and
only two groups exist in flame coal and anthracite. The EPR spectrum of medium-rank coal is a superposition of two broad and
two narrow lines. Both broad and narrow, and two narrow lines were measured in EPR spectra of flame coal and anthracite, respectively.
Two types of paramagnetic centres with broad lines and one group with narrow lines exist in exinite and vitrinite from medium-rank
coal. Two narrow components were observed in EPR spectra of its inertinite. Two different broad electron paramagnetic resonance
signals were detected for macerals from low-coalificated coal. Paramagnetic centres systems of medium-rank coal samples reveal
the most complex character. Broad EPR lines were not observed for the higher coalificated samples, i.e., anthracite and inertinite
from medium-rank coal. Narrow lines do not occur in EPR spectra of low-coalificated macerals. Strong dipolar interactions
and fast spin-lattice relaxation processes are characteristic for paramagnetic centres with broad lines. Strong exchange interactions
and short spin-lattice relaxation time were measured for paramagnetic centres with the narrowest EPR signals. 相似文献