Electron paramagnetic resonance study of Fe3+ centres in KTiOAsO4

An EPR study of Fe³⁺ centres in single crystal KTiOAsO₄ (KTA) has been performed at the Q-band frequency. Two Fe³⁺ centres have been observed for which all spin-Hamiltonian parameters were calculated. The comparison of the pseudosymmetries obtained from fourth-order constants of the spin-Hamiltonian and from a fourth-order crystal field calculation for the two Ti-octahedra, allowed us to locate one Fe³⁺ at both Ti sites in KTA. The deviation from cubic symmetry is similar and not very large for the two centres showing that the charge compensation mechanism is not at short distance.     

Electron Paramagnetic Resonance and Mössbauer Studies of Fe3+ Ions in the Fe2O3 [dbnd] MoO3 System

The electron paramagnetic resonance (EPR) and Mössbauer spectra of ironmolybdenum mixed oxides system have been investigated. Both EPR and Mössbauer measurements revealed the formation of ferric molybdate, Fe₂ (MoO₄)₃ and the existence of two different Fe³⁺ species. The EPR spectra of Fe₂ (MoO₄)₃, show two resonance lines of Fe³⁺ ions indicating that a strong exchange interaction is dominates in pure iron molybdate. Mösbauer measurements revealed that the isomer shift (I. S) increases with increasing the iron content. A maximum of quadrupole splitting (Q. S) is observed at the stoichiometric concentration corresponding to the formation of Fe₂ (MoO₄)₃. The effect of a catalytaic dehydration process on the redox behaviour of Fe³⁺ located in iron molybdate frame work is investigated. Results indicate that the catalytaic dehydration of 2-proppanol over this catalyst reduces Fe³⁺ ions to Fe²⁺ leading to the formation of the inactive phase FeMoO₄. the essential role of oxygen, in the alcohol gas feed, in regeneration the activity of the catalysts was demonstrated.     

Absorption,luminescence, and electron paramagnetic resonance of molybdenum ions in CdWO4

A single crystal of cadmium tungstate (CdWO₄) containing approximately 200 ppm of molybdenum was grown by the Czochralski method and then characterized in a series of optical absorption, photoluminescence (PL), photoluminescence excitation (PLE), and electron paramagnetic resonance (EPR) experiments. The Mo⁶⁺ ions substitute for W⁶⁺ ions and serve as recombination sites for electrons and holes when the crystal is exposed to ionizing radiation. A charge-transfer absorption band for the Mo⁶⁺ ions was observed near 320 nm at 10 K. The PL experiments, performed at low temperature with 325 nm excitation, showed a Mo-associated emission peaking near 680 nm. A direct correlation of the 680 nm emission and the 320 nm absorption band was established by the PLE data. When these doped CdWO₄ crystals are exposed at low temperature either to light that is near or above the band gap or to X-rays, the Mo⁶⁺ ions can trap an electron and form stable Mo⁵⁺ ions. The EPR spectrum of the Mo⁵⁺ ions was observed at temperatures near 15 K, and a complete set of parameters describing the g matrix was obtained from an angular dependence study.     

A comparison of calculated and measured hyperfine structure of epr spectra of Mn2+ ion in LiNbO3 monocrystal

An outline of numerical calculation of positions and intensities of spectral lines in EPR spectra of Mn²⁺ ion in LiNbO₃ is presented. Results of numerical calculations obtained by means of computers TESLA 200 and SIEMENS 4004 are compared with experimental spectra. A modification of Jacobi's method of diagonalization is described, which was used for exact solution of a secular equation with Hermitian matrix.     

Optical and luminescence properties of CdWO4 and CdWO4:Mo single crystals

Luminescence properties of a pure CdWO₄ crystal and a CdWO₄:Mo crystal doped with molybdenum in different concentrations have been investigated. The effect of molybdenum impurity on the intrinsic luminescence of CdWO₄ has been found, and the role of the impurity in the formation of new luminescence centers has been investigated. The features of the formation of the intrinsic and impurity luminescence excitation spectra of CdWO₄ and CdWO₄:Mo crystals in the fundamental-absorption region have been considered. The reflection spectra of the CdWO₄ crystal have been investigated taking into account the crystal structure anisotropy.     

Muon level crossing resonance of the R3NMu+ ion

Observation of muon level crossing resonance with¹⁴N nuclei in frozen triethylamine is reported and assigned to the ionic species (C₂H₅)₃NMu⁺. In forming this species, the implanted positive muons mimic the chemical behaviour of protons as usual, here in a process analogous to the protonation of a base. The resultant molecular ion has the axial symmetry necessary for detection of level crossing with an integral-spin nucleus. The quadrupole coupling constant is determined to be ¦e ² qQ/h¦=0.41(4) MHz, corresponding to an electric field gradient on¹⁴N of 0.10(1) a.u. and consistent with anab initio estimate for species of the type R₃NMu⁺. The prospects for detection of the muonium-substituted ammonium ion NH₃Mu⁺ ion in ammonia are discussed.     

Nonlinear properties of Pb5Ge3O11:Gd3+ in an electric field: Paramagnetic resonance

This paper discusses the field and temperature dependences of the shift in position of EPR signals in an external electric field, which is linearly related to the polarization in the paraelectric phase of Pb₅Ge₃O₁₁:Gd³⁺. Fiz. Tverd. Tela (St. Petersburg) 39, 1643–1644 (September 1997)     

Paramagnetic faraday effect in Ce3+:YAG

The author thanks Josef Kvapil for supplying the samples and J. Hakenová for experimental assistance.     

Paramagnetic resonance results on a tetragonal Eu2+ center in SrFCl crystals

This letter reports the results of the EPR investigation of an Eu²⁺ center in SrFCl crystals. The Eu²⁺ ion substitutes for a cation in the otherwise locally unperturbed crystal.     

Paramagnetic resonance in phosphorescent aromatic hydrocarbons

Electron resonance spectra have been recorded of the lowest triplet states of benzene, toluene, triptycene and tribenzotriptycene. The experiments were carried out by ultra-violet irradiation of these molecules in rigid glass solutions both at 77°k and 20°k. From an analysis of the line shape of the spectra, which prove to be strongly temperature dependent, the following conclusions could be drawn.

Benzene in its first triplet state has a configuration of lowest energy which is not a regular hexagon. This finding, supported by the results for toluene, was substantiated by SCF-MO calculations; it is in agreement with a recent analysis by Liehr and Moffitt. Tunnelling between equivalent conformations of benzene is thought to occur at a rate of the order of 10⁹–10¹⁰ sec^-1.

The spectra of the phosphorescent states of triptycene and tribenzotriptycene are dominated by intramolecular excitation transfer between the benzene or naphthalene sub-systems. In triptycene at 77°k transfer occurs at a rate ? 10¹⁰ sec^-1, so that one observes the resonance signal of a triplet exciton. In tribenzotriptycene the transfer is somewhat slower. The rate of excitation transfer decreases with temperature and at 20°k most of the excitation in tribenzotriptycene is effectively trapped in the naphthalene sub-systems.     

Paramagnetic resonance of the (Cr5+O4)H2 Halperin-Varma center in NH4H2AsO4 and KH2AsO4

The electron paramagnetic resonance (EPR) spectrum of Cr⁵⁺(3d ¹,S=1/2) in undeuterated and 58%-deuterated NH₄H₂AsO₄ was investigated. The EPRg-value tensors in the paraelectric and antiferroelectric phases are almost the same as those observed at high and low temperatures in KH₂PO₄ and KH₂AsO₄. This shows that the (Cr⁵⁺O₄)H₂ complex is the same in all crystals, i.e., a wave function ofd _x ²–y ² character coupled to two lateral protons which reorient among the four possible Slater configurations in the paraelectric phase. The remarkable isotope shift of the local dynamic reorientational slowing-down observed in KH₂PO₄ and KH₂AsO₄ in approximate proportion to the shift of the bulk ferroelectric transition temperaturesT _c ^F , and the antiferroelectricT _c ^AF of NH₄H₂AsO₄, is analyzed qualitatively. It is shown to result mainly from the isotope effect of the short-range interactionJ _sr via protons and deuterons for the impurity and for the bulk. Q-band data of the (Cr⁵⁺O₄)H₂ center in 75%-deuterated KH₂AsO₄ are also reported. An averaged high- and nonaveraged low-temperature EPR spectrum is observed in a temperature range of 250 to 290 K. The intensity ratio of the two follows an exp 2(T—T)/ law over four orders of magnitude atT=266 to 273 K and=5.3 to 6.1 K depending on the orientation of the external magnetic field. This novel result in motional narrowing is analyzed analytically to be compatible with a distributionP _A of ₀(T, T, ) of half width, in reorientation times withE=0.23 ±0.02 eV, , probably resulting from the statistical occupation of deuterium atoms among the O—–H–O bridges. Comparison with a theory of Binder definitely proves the extrinsic slowing-down and thus Halperin-Varma type character. In the range of temperatures investigated no local freeze-out has been detected.     

光谱法研究1,3-硫杂杯[4]罗丹明乙二胺酰胺衍生物对Fe3+的探针性能

利用硫杂杯[4]芳烃衍生物与罗丹明乙二胺发生酰化反应,合成了2个具有双罗丹明基团的1,3-硫杂杯[4]罗丹明乙二胺酰胺衍生物.在实验条件下,衍生物与Fe3+均能形成1:1配合物,配合物的形成诱导了衍生物分子中罗丹明基螺环开环,而表现出良好的荧光和比色探针性能.1,3-硫杂杯[4]罗丹明酰胺-2,4-酯对Fe3+的选择性...     

Paramagnetic resonance of yttrium aluminum garnet doped with 151Eu2+ ions

Physics of the Solid State - The 151Eu2+ orthorhombic centers in yttrium aluminum garnet crystals have been investigated. The initial splitting and hyperfine interaction parameters have been...