Magnetic Resonance Study of Fe-Implanted TiO<Subscript>2</Subscript> Rutile

Single-crystal (100) and (001) TiO₂ rutile substrates have been implanted with 40 keV Fe⁺ at room temperature with high doses in the range of (0.5–1.5) × 10¹⁷ ions/cm². A ferromagnetic resonance (FMR) signal has been observed for all samples with the intensity and the out-of-plane anisotropy increasing with the implantation dose. The FMR signal has been related to the formation of a percolated metal layer consisting of close-packed iron nanoparticles in the implanted region of TiO₂ substrate. Electron spin resonance (ESR) signal of paramagnetic Fe³⁺ ions substituting Ti⁴⁺ positions in the TiO₂ rutile structure has been also observed. The dependences of FMR resonance fields on the DC magnetic field orientation reveal a strong in-plane anisotropy for both (100) and (001) substrate planes. An origin of the in-plane anisotropy of FMR signal is attributed to the textured growth of the iron nanoparticles. As result of the nanoparticle growth aligned with respect to the structure of the rutile host, the in-plane magnetic anisotropy of the samples reflects the symmetry of the crystal structure of the TiO₂ substrates. Crystallographic directions of the preferential growth of iron nanoparticles have been determined by computer modeling of anisotropic ESR signal of substitutional Fe³⁺ ions.     

Effects of Gd<Superscript>3+</Superscript> doping on structural and dielectric properties of PZT (Zr:Ti = 52:48) piezoceramics

The purpose of this research is to study the effect of doping Gd into Pb(Zr_0.52Ti_0.48)O₃ ceramics prepared by solid state reaction. X-ray diffraction patterns show that all PGZT samples are of tetragonal structure and the highest doping should be no more than 2 mole % Gd at which the unreacted oxides start to appear. The electron spin resonance (ESR) spectra of PGZT's indicate that Gd³⁺ can enter both A site of the perovskite structure instead of only A site as widely believed. The ESR peaks resonance shift towards low fields as the concentration is higher, which is due to the change in crystal field experienced by Gd³⁺ ions. At x =0.001, 0.005 and 0.01 dopings, two sets of powder ESR signals arising from Gd³⁺ (4f⁷, spin 7/2) ions at A site. The first set shows some fine structure having strong absorption peaks centered at 76.26 mT (g = 8.550). The second is a seven-peak spectrum centered at 206.01 mT (g = 3.165), which belongs to the Gd³⁺ ions at B sites. Furthermore, the overlapped ESR strong absorption peaks from 309.17 mT to 314.49 mT (g = 2.2818-2.1087) belong to Gd³⁺ of unreacted Gd₂O₃. The local environments of Gd³⁺ ions were verified from the calculated ESR spectra using appropriate spin Hamiltonian parameter, i.e. gyromagnetic tensor g, zero-field splitting D and hyperfine tensor A.     

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.     

Growth defect W<Superscript>3+</Superscript>-W<Superscript>2+</Superscript> of CdWO<Subscript>4</Subscript> crystals

CdWO₄ crystals grown by the Czochralski method at the low-temperature gradient were investigated with electron spin resonance (ESR) spectroscopy. ESR spectra did not contain the spectra of impurity ions typical for the CdWO₄ structure, i.e., Fe³⁺, Mn²⁺, and Cr³⁺. At the same time, in the studied crystals a complex ESR spectrum having the hyperfine structure due to two nonequivalent tungsten atoms was observed (W¹⁸³;I=1/2; natural abundance, 14.28%). Angular dependence analysis and simulation of ESR spectra have shown that this novel spectrum is described by a spin-Hamiltonian with the following parameters:D=839 G,E=80 G,g _xx=2.01,g _yy=1.97,g _zz=1.987 and electron spinS=7/2. There is one magnetically nonequivalent position of the center in the crystal structure and the direction ofD _zz andg _zz corresponds to the direction of W_n-W_n+2 (or Cd_n-Cd_n+2) in the crystal structure. Because of the fact that it is in principle impossible to achieve the electron stateS=7/2 for the d-shell of one transition metal ion and taking into account the fact that such electron state is realized for two nonequivalent tungsten atoms, we suppose the defect structure to be the chain W²⁺-M⁺-W³⁺. In the structure of this defect the ion M⁺ is diamagnetic, the ions W²⁺ and W³⁺ have electron spinS=2 andS=3/2, respectively. The necessary condition for such defect to exist is to place this chain of ions in cadmium positions for the charge compensation. the reason for such defects to form is supposed to be the incorporation of M⁺ ions into the CdWO₄ lattice. The presence of W²⁺ and W³⁺ in Cd positions in the defect structure provides the charge compensation and the lowering of the lattice stress.     

Electron paramagnetic resonance study of Fe<Superscript>3+</Superscript> ions at octahedral and tetrahedral mirror symmetry sites in the LiScGeO<Subscript>4</Subscript> crystal

An electron paramagnetic resonance (EPR) study of a synthetic single crystal of LiScGeO₄ doped with Cr ions carried out earlier at the X- and Q-bands at 300, K has indicated additional weak lines. A detailed analysis of these EPR lines, which were tentatively attributed to the Fe³⁺ ions at two different mirror symmetry sites, is presented in this paper. The angular dependences in the three crystallographic planes were resolved by fitting the two distinct spectra denoted Fe³⁺(I) and Fe³⁺(II) with a spin Hamiltonian (S=5/2) of monoclinic symmetry. The rank-4 crystal field tensors at tetrahedral and octahedral sites were calculated with the point-charge model to determine the principal axis orientations of their cubic, tetragonal and trigonal components. A comparative analysis of the zero-field splitting tensors and the crystal field ones indicates that Fe³⁺(I) ions substitute for Sc³⁺ at octahedral sites and Fe³⁺(II) ions substitute for Ge⁴⁺ at tetrahedral sites with no significant distorition of the coordination polyhedra in the structure of LiScGeO₄.     

Electron paramagnetic resonance of Cr<Superscript>3+</Superscript> ions in ABO<Subscript>3</Subscript> (A = Sc,Lu, In) diamagnetic crystals

A magnetic resonance method is applied to the investigation of a number of isostructural diamagnetic compounds ABO₃ (A = Sc, Lu, In) with small additions of Cr³⁺ ions (S = 3/2) sufficient to observe single-ion spectra. It is shown that the resonance spectra for isolated Cr³⁺ ions can be described to a good accuracy by the ordinary axial spin Hamiltonian for 3d ions in octahedral oxygen environment. The parameters of the spin Hamiltonian are determined. It is established that Cr³⁺ ions in these crystals are characterized by easy-axis-type anisotropy.     

ESR signals from clusters of iron ions as indicators of the thermal history of fault gouge

Samples taken from four different faults at a depth of 400 m show no sign of a bulk heating higher than about 350°C (heating time 15 min) during fault activities. Besides radiation defects, the aggregation behavior of iron ions studied by electron spin resonance (ESR) can be used as a measure for the thermal history of fault gouge material. Clusters of iron ions are formed as a result of the heating of biotite and feldspar minerals. They give broad (ΔB ≈ 200 mT) and intense signals in the ESR spectra. Mn²⁺ point defects react very sensitively to crushing of the samples, while relatively isolated and coupled Fe³⁺ point defects in the feldspars do not.     

Quantum registers based on single NV + <Emphasis Type="Italic">n</Emphasis><Superscript>13</Superscript>C centers in diamond: I. The spin Hamiltonian method

Details of the application of the spin Hamiltonian method for studying spin characteristics of a quantum register that includes an electron spin S = 1 of a single NV center in the ground electronic state and nuclear spins I = 1/2 of several isotopic atoms ¹³C located at different lattice sites near the vacancy of the NV center. Two methods of finding the hyperfine interaction tensors for these NV + n ¹³C spin systems are considered, one of which is based on the conventional electron spin resonance (ESR) method, while the other involves methods of quantum chemistry. The results of the latter method are compared with ESR data and with spectra of optically detected magnetic resonance (ODMR) and with the character of the modulation of the ODMR echo decay observed in single NV + n ¹³C systems. This comparison shows that the ab initio modeling of the spin characteristics of diamond nanoclusters containing NV centers makes it possible to obtain quantitative spin characteristics of the quantum registers under study.     

Magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> surface

The magnetic properties of the magnetite Fe₃O₄(110) surface have been studied by spin resolved Auger electron spectroscopy (SRAES). Experimental spin resolved Auger spectra are presented. The results of calculation of Auger lines polarization carried out on the basis of electronic state density are presented. Problems related to magnetic moments of bivalent (Fe²⁺) and trivalent (Fe³⁺) ions on the Fe₃O₄(110) surface are discussed. It is established that the deposition of a thin bismuth film on the surface results in significant growth of polarization of iron Auger peaks, which is due to additional spin-orbit scattering of electrons by bismuth atoms.     

Exchange-coupled pairs of Fe3+ ions in beryl

The EPR spectrum of first nearest neighbour pairs of Fe³⁺ ions substituting for Al³⁺ ions in beryl is reported. The form of the pair spin Hamiltonian is discussed, and operator equivalent factors for fourth-order terms are tabulated. The Fe³⁺ pair interionic coupling corresponds to isotropic antiferromagnetic exchange with J = + 1.7 cm^-1 plus anisotropic dipolar coupling. The pair value of the zero-field splitting parameter D is + 0.0206 cm^-1 and shows a substantial shift from the single-ion value. It is proposed that resonance lines previously attributed to Fe³⁺ ions in Be²⁺ or Si⁴⁺ sites are due to Fe³⁺ pairs.     

Electron spin resonance investigation of the substitution of Fe3^＋ for Ti4^＋ ions in rutile TiO2 single crystal

A Fe doped rutile TiO 2 single crystal is grown in an O 2 atmosphere by the floating zone technique.Electron spin resonance (ESR) spectra clearly demonstrate that Fe 3+ ions are substituted for the Ti 4+ ions in the rutile TiO 2 matrix.Magnetization measurements reveal that the Fe:TiO 2 crystal shows paramagnetic behaviour in a temperature range from 5 K to 350 K.The Fe 3+ ions possess weak magnetic anisotropy with an easy axis along the c axis.The annealed Fe:TiO 2 crystal shows spin-glass-like behaviours due to the aggregation of the ferromagnetic clusters.     

Theoretical studies of absorption spectra and microstructure of Ni2+ at the octahedral site of the NiFe2O4 nanoparticle

The optical absorption spectra, microstructure and electronic spin resonance parameters (electronic spin resonance (ESR) g factor) for Ni²⁺ ions at octahedral centers of nickel ferrite nanoparticles are calculated from the two-spin–orbit-parameter model. The effect of spin–orbital coupling of the central metal 3d⁸ ions and ligand oxygen ions has been taken into account in the full energy matrix and ESR g formula. The calculated results are in good agreement with the observed values. In addition, the microstructures of Ni²⁺ ions at octahedral centers in NiFe₂O₄ are reasonably determined from the calculations.     

Effects of high-temperature annealing on ESR properties of solid solutions of garnet minerals

A garnet (G7) silicate mineral belonging to pyralspite subgroup was studied using the technique of electron spin resonance (ESR). This study shows that iron is present in G7 as isolated species as well as species coupled by dipolar interactions. The ESR data shows a gradual increase of cluster of Fe³⁺ ions accompanied by decrease of dipolar interactions and increase of possible exchange interactions at high temperature. The Fe²⁺→Fe³⁺ oxidation process occurs in the garnets as a function of annealing temperature. Thermoluminescence (TL) peaks at approximately 190 and 340 °C are observed in the irradiated G7 garnet. Investigations using the technique of ESR were carried out to identify the centers involved in the TL process.     

ESR experiments with egg shells of chickens

The electron spin resonance spectra fromGallus domesticus egg shells exhibit a strong free radical singlet, a spectrum due to Mn²⁺ ions in a calcite site, a low field line line atg≈30/7 due to Mn²⁺ in a rhombic site, and spectral lines arising from Fe³⁺ ions. Details of the ESR spectral lines did not correlate with fertile, non-fertile or color type egg-shell characteristics.     

Paramagnetic resonance of Mn<Superscript>4+</Superscript> and Mn<Superscript>2+</Superscript> centers in lanthanum gallate single crystals

An increase in the manganese concentration in lanthanum gallate in the range 0.5–5.0% has been found to result in a complete replacement of individual Mn⁴⁺ ions by Mn²⁺ ions. The relative concentrations and binding energies of individual Mn⁴⁺, Mn³⁺, and Mn²⁺ ions have been determined. The spin Hamiltonians of the Mn²⁺ and Mn⁴⁺ centers in the rhombohedral and orthorhombic phases, respectively, have been constructed and the orientation of the principal axes of the fine-structure tensor of Mn⁴⁺ at room temperature has been found. The possibility of using electron paramagnetic resonance for determining the rotation angles of oxygen octahedra of lanthanum gallate with respect to the perovskite structure has been discussed.     

Gamma ray interactions with MoO3-doped lead phosphate glasses

The UV–Visible, Fourier transform infrared (FTIR) and Raman and electron spin resonance (ESR) spectra of undoped lead phosphate and MoO₃-doped glassy samples have been investigated. The UV–VIS absorption spectra were re-measured after successive gamma irradiation. Before irradiation, undoped sample exhibited strong ultraviolet absorption, which was attributed to co-absorption due to trace iron impurities (mainly Fe³⁺ ions) and lead Pb²⁺ ions. With the introduction of MoO₃ in progressive amounts, extra visible bands were recorded at about 400–440, 540, 750 and 870?nm. These bands are most likely correlated with the presence of Mo³⁺, Mo⁴⁺ and Mo⁵⁺ ions in the host glass. In the undoped specimen, gamma irradiation produced UV absorption bands that increased slightly with irradiation but no visible bands were recorded. Samples containing high MoO₃ content showed some resistance to irradiation with no bands in the visible region being observed. FTIR absorption spectra of the undoped and MoO₃-doped samples revealed the formation of metaphosphate and pyrophosphate structural units. Highly MoO₃-doped samples exhibited additional bands due to molybdate groups. Raman and ESR spectra were in agreement with UV–VIS and IR data, indicating the presence of molybdenum ions in lead phosphate glass, as Mo³⁺, Mo⁴⁺ and Mo⁶⁺ with different ratios. However, such glassy systems favor the trivalent species.     

EPR studies of Cu<Superscript>2+</Superscript>-doped bis(saccharinato)bis(pyridine)zinc(II) single crystals

The electron paramagnetic resonance spectra of Cu²⁺ impurities in bis(saccharinato)bis(pyridine)zinc(II) single crystals have been studied at room temperature in three mutually perpendicular planes. The angular variation of the spectra indicates the substitution of the host Zn²⁺ with Cu²⁺. Two magnetically inequivalent sites for Cu²⁺ have been observed. The spectra were fitted to the rhombic spin Hamiltonian. The spin Hamiltonian parameters and the molecular orbital coefficients were evaluated for the two sites. The ground-state wave function of Cu²⁺ ion in the lattice has been constructed.     

Bay Functionalized Perylenediimide with Pyridine Positional Isomers: NIR Absorption and Selective Colorimetric/Fluorescent Sensing of Fe<Superscript>3+</Superscript> and Al<Superscript>3+</Superscript> Ions

Bay functionalized perylene diimide substituted with pyridine isomers, (2-pyridine (2HMP-PDI), 3-pyridine (3-HMP-PDI) and 4-pyridine (4-HMP-PDI)) have been synthesized and explored for selective coloro/fluorimetric sensing of heavy transition metal ions. HMP-PDIs showed strong NIR absorption (760–765 nm) in DMF. The absorption and fluorescence of HMP-PDIs have been tuned by make use of pyridine isomers. Reddish-orange color was observed for 2-HMP-PDI (λ_max = 437, 551, 765 nm) whereas 4-HMP-PDI exhibited light green (λ_max = 432, 522, 765 nm). 3-HMP-PDI showed orange-yellow (λ_max = 431, 524, 762 nm). The fluorescence spectra of 2-, 3- and 4-HMP-PDI showed λ_max at 585, 538, 546 nm, respectively. Interestingly, HMP-PDI dyes showed selective color change (intense pink color) and fluorescence quenching for Fe³⁺ and Al³⁺ metal ions in DMF. Absorbance spectra revealed complete disappearance of NIR absorption and intensification/appearance of new peak at lower wavelength. The concentration dependent studies suggest that 4-HMP-PDI can detect up to 36.52 ppb of Fe³⁺ and 43.12 ppb of Al³⁺ colorimetrically. The interference studies in presence of other metal ions confirmed the good selectivity for Fe³⁺ and Al³⁺. The mechanistic studies indicate that Lewis acidic character of Fe³⁺ and Al³⁺ ions were responsible for selective color change and fluorescence quenching.     

Electron Spin Resonance and Ground State Wave Functions of Vanadyl Ion in LiNaSO<Subscript>4</Subscript>

Electron spin resonance (ESR) of VO²⁺ doped into LiNaSO₄ has been studied at 300 K on an X-band spectrometer. The ESR powder spectra have been analyzed and spin Hamiltonian parameters have been evaluated. Using the crystal-field approach, a theoretical estimate of the ground state wave functions of VO²⁺ in LiMSO₄ (M = Na, K) has been made from the ESR data. The dipolar hyperfine coupling constant P and Fermi contact parameter K have also been estimated.     

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.