Theory studies of the local lattice distortions and the EPR parameters for Cu2+, Mn2+ and Fe3+ centres in ZnWO4

The local lattice distortions and the electron paramagnetic resonance (EPR) parameters (g factors, hyperfine structure constants and zero-field splittings) for Cu²⁺, Mn²⁺ and Fe³⁺ in ZnWO₄ are theoretically studied based on the perturbation calculations for rhombically elongated octahedral 3d⁹ and 3d⁵ complexes. The impurity centres on Zn²⁺ sites undergo the local elongations of 0.01, 0.002 and 0.013 Å along the C₂ axis and the planar bond angle variations of 8.1°, 8.0° and 8.6° for Cu²⁺, Mn²⁺ and Fe³⁺, respectively, due to the Jahn–Teller effect and size and charge mismatch. In contrast to the host Zn²⁺ site with obvious axial elongation (～0.31 Å) and perpendicular (angular) rhombic distortion, all the impurity centres demonstrate more regular octahedral due to the above local lattice distortions. The copper centre exhibits significant Jahn–Teller reductions for the spin-orbit coupling and orbital angular momentum interactions, characterised by the Jahn–Teller reduction factor J (≈0.29 ? 1). The calculated EPR parameters agree well with the experimental results. The local structures of the impurity centres are analysed in view of the corresponding lattice distortions.     

Emission properties of Eu, Mn in MAl2Si2O8 (M=Sr, Ba)

The emission properties of Eu²⁺ and Mn²⁺ in monoclinic SrAl₂Si₂O₈ (M-SAS) and hexagonal BaAl₂Si₂O₈ (H-BAS), both of which have only one alkaline-earth site, were studied. The emission peaks of both Eu²⁺ (405 nm) and Mn²⁺ (564 nm) in SrAl₂Si₂O₈, are located at longer wavelengths, compared with those in H-BAS (373 nm for Eu²⁺ and 518 nm for Mn²⁺), because of the stronger crystal field strength at the Sr site. EPR spectra showed that the g values of Mn²⁺ are 4.5065 in M-SAS:Mn and 2.0247 in H-BAS:Mn. Magnetic measurements proved that Mn²⁺ was at high-spin state in both hosts. The large g value of Mn²⁺ in M-SAS was ascribed to the mixing of the first excitation state to the ground state, both of which have lower d orbital degeneracy due to the lower symmetry of Mn²⁺ site. The transfer efficiency from Eu²⁺ to Mn²⁺was about 10% in M-SAS, higher than that in H-BAS (5%). This was probably because Eu²⁺ emission overlaps the relatively low excitation level of Mn²⁺ in M-SAS. In order to obtain high transfer efficiency, it was necessary for the Eu²⁺ emission to overlap the lowest excitation level of Mn²⁺. The results obtained in this work may be helpful to design the new white or red phosphors for white-light emitting diode (w-LED) applications.     

Synthesis and characteristics of natural zeolite supported Fe-TiO2 photocatalysts

Natural zeolite supported Fe³⁺-TiO₂ photocatalysts were synthesized for the sake of improving the recovery and photocatalytic efficiency of TiO₂. The as-prepared materials were characterized by X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible diffuse reflection spectroscopy (UV-vis DRS), scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDX). Methyl orange was used to estimate the photocatalytic activity of the samples. The results showed that zeolite inhibited the growth of TiO₂ crystallite sizes. The Fe³⁺ concentration played an important role on the microstructure and photocatalytic activity of the samples. The iron ions could diffuse into TiO₂ lattice to the form Fe-O-Ti bond and gave TiO₂ the capacity to absorb light at lower energy levels. The photocatalytic activity of the samples could be enhanced as appropriate dosages of Fe³⁺ were doped.     

Mn, Cr-co-doped MgAl2O4 phosphors for white LEDs

The Mn-, Cr-doped and Mn, Cr-co-doped MgAl₂O₄ powders have been synthesized via a gel-solid reaction method. Energy transfer from Mn²⁺ to Cr³⁺ has been observed for the first time in the co-doped MgAl₂O₄ phosphors. When excited with blue light with a wavelength of 450 nm at room temperature, both green emission from Mn²⁺ around 520 nm and red emission from Cr³⁺ around 675and 693 nm were generated. Moreover, the color of the emission can be modified by controlling the doping concentrations of Mn²⁺ and Cr³⁺. Therefore, MgAl₂O₄: Mn²⁺, Cr³⁺ could be used as a single-phased phosphor for white LED with a blue LED chip. The energy transfer in terms of Mn²⁺ to Cr³⁺ is determined by means of radiation and reabsorption.     

Luminescence of BaAl2O4:Mn,Ce phosphor

Powder samples of barium aluminate doped with Mn²⁺ and Ce³⁺ were prepared by solid-state reaction method and their photoluminescence and thermoluminescence properties were studied. Substitution of Ca/Sr in place of Ba resulted in enhanced emission from Ce³⁺ ions without changing the spectral profile. Cerium efficiently sensitized the manganese luminescence in barium aluminate. Photoluminescence and thermo luminescence observations have indicated the presence of V_k³⁺ defects in undoped barium aluminate. However, Barium aluminate (either undoped or doped with manganese) did not exhibit long afterglow.     

Iron ions in ZSM-5 zeolite: Fe3+ in framework, Fe2+ in extra-framework positions in catalytic N2O decomposition

Fe-ZSM-5 samples containing a combination of ⁵⁷Fe³⁺ in framework (FW) and regular iron in extra-framework (EFW) sites were prepared by introducing ⁵⁷Fe in hydrothermal synthesis, then exchanging Fe²⁺ of natural isotope composition into the lattice. The stability for one part of Fe²⁺ and Fe²⁺ ? Fe³⁺ reversibility for the other part in catalytic decomposition of N₂O is demonstrated by in situ Mössbaer measurements. Formation of dinuclear Fe_FW–O–Fe_EFW pairs is not prevailing.     

Mechanism of enhanced photocatalysis of TiO2 by Fe in suspensions

In this work, the mechanism of enhanced photocatalysis of TiO₂ with Fe³⁺ was studied using Sulfadiazine (SD) as the model compound. Results indicated that degradation rate of SD was enhanced by the addition of Fe³⁺ in TiO₂ suspension. The crystalline structure of TiO₂ particles was stable in suspensions. The hydroxyl radical generated by TiO₂/Fe³⁺ (both TiO₂ and Fe³⁺) photocatalysis was in a higher yield. Moreover, Fe²⁺ was found not to give an obvious impact on the SD degradation in TiO₂ suspension, whereas Fe³⁺ had a notable effect. The adsorption amount of TiO₂ was greatly enhanced by the addition of Fe³⁺ in suspensions. Finally, an interaction model of SD degradation in TiO₂ suspension containing Fe³⁺ was also proposed by investigating of surface behaviors of TiO₂ particles. It will be beneficial to use Fe³⁺ as the electron acceptors on the surface of TiO₂ particles, which helps to improve the yield of hydroxyl radical.     

Application of solid state track recorders for neutron spectra measurements in a reactor irradiation facility

Abstract

In connection with the IAEA-neutron seed irradiation Programme, a standard neutron irradiation facility has been constructed. The application of solid state track recorders for fast neutron spectra measurements inside this facility is discussed. Fissionable targets of ²³⁵U, ²³⁹Pu, ²³⁷Np, ²³⁸W and ²³²Th will be used, an approximative solution for the incident neutron spectrum will be obtained by a five-group method.     

An EPR Study on the Chemical form of Mn2+ in the Chinese Loess Samples

Electron paramagnetic resonance (EPR) spectroscopy in combination with thermal methods were used to identify and characterize Mn²⁺ in the Chinese loess that is a multimineral system. EPR spectra of the loess samples from the classic loess-paleosol section in central China show the presence of trace amounts of Mn²⁺; whereas paleosol samples present no Mn²⁺ EPR signal. The spectral changes upon step heating from room temperature to 1000 °C suggest that this EPR signal in the loess arises from Mn substituted into CaCO₃. This study provides a direct evidence that the loess-paleosol profiles were formed under the changing redox conditions caused by a past climatic change.     

Optical characterization of Mn, Ni and Co ions doped zinc lead borate glasses

This paper reports on the development and optical characterization of heavy metal oxide (HMO)-based transparent glasses in the chemical composition of 15PbO-40B₂O₃-(45−x) ZnO−x TM²⁺ (=Mn²⁺ or Ni²⁺ or Co²⁺) (where x=0.2, 0.5 mol%). For these glasses both absorption and emission spectra have been measured, in order to understand their optical performances. The XRD profiles have confirmed their glassy nature and the FTIR spectral features have been analyzed. From the emission spectra, a bright green emission (538 nm) from Mn²⁺-glasses, an intense red emission (670 nm) from Ni²⁺ and from Co²⁺ (625 nm) glasses have been noticed very clearly. Based on the UV-absorption spectra of these materials, both direct and indirect bond gaps have been computed. Apart from the spectral analysis, different physical properties of these glasses have also been carried out. Due to the presence of both PbO and ZnO, these glasses are found to be good moisture-resistant optical systems. Both optical and physical properties have been found to be more encouraging towards their use as novel luminescent optical materials.     

Photographic sensitivity of silver halide emulsions (on the light-intensity factor determining the mechanism of chemical sensitization)

Some evidence which indicates that the role of chemical sensitization is different for exposures to low and to high intensities have been demonstrated with a model emulsion. This paper presents a review of several published reports and offers some new information. The author concludes that the sensitivity specks on the surface of the grains are responsible for sensitivity at high intensities, whereas the silver-ion gelatin complexes and a small group of silver-atoms surrounded by gelatin attached to the grain surface are responsible for sensitivity at low intensities.     

White light generation through the zinc metaphosphate glass activated by Ce, Tb and Mn ions

The photoluminescence of Ce³⁺, Tb³⁺ and Mn²⁺ ions was investigated in the Zn(PO₃)₂ glass. The blue and green emissions of Tb³⁺ ions and the red emission of Mn²⁺ ions are enhanced upon UV excitation through a non-radiative energy transfer from Ce³⁺ to Tb³⁺ and Mn²⁺ ions. The efficiency of this transfer was estimated in at least 62%. It is demonstrated that this glass activated with three ions (Ce³⁺, Tb³⁺ and Mn²⁺) can generate white light emission (x=0.420 and y=0.423 chromaticity coordinates and 3440 K colour temperature) under excitation at 254 nm, i.e., using an AlGaN-based LED as excitation source.     

Fluorescence and persistent spectral hole burning of Eu in Ge-Ga-S-KBr glasses

Fluorescence and efficient persistent spectral hole burning of Eu³⁺ at 77 K were observed in chalcohalide glasses. The depth of the hole was approximately 30% after a burning process of 1 min with 50 mW power, and it was completely erased with Ar⁺ laser irradiation. The hole survived room temperature heat treatment and showed good thermal stability. The hole-burning mechanism was most probably the photo-reduction of Eu³⁺→Eu²⁺. Fluorescence from Eu³⁺ decreased with increasing temperature and disappeared at the temperature above ∼130 K.     

Thermoluminescence spectroscopy of Eu and Mn doped BaMgAl10O17

Thermoluminescence (TL) studies of Eu²⁺ and Mn²⁺ doped BaMgAl₁₀O₁₇ (BAM) are reported and discussed. The TL spectra that are measured after irradiation with ultraviolet (120-) show a series of TL peaks between 100 and . The TL spectra are similar for BAM with the two dopants, which suggest that the shallow traps are typical for the BAM host lattice. Using the Hoogstraaten analysis trap depths between 0.1 and are determined. A model is proposed based on thermally activated recombination in local TL centres (not via the conduction band). Further support for this model is obtained from the observation that the TL signal is strongest for excitation around the band edge of BAM . Upon heating the samples in air all low temperature TL peaks decrease in intensity. In addition a new peak appears in the TL spectrum, which is connected with a deeper trap and also a partial oxidation of Eu²⁺ to Eu³⁺ is observed. The luminescence efficiency is lower and the UV induced degradation is faster after annealing in air. These results indicate that the shallow traps are related to oxygen vacancies. The shallow traps do not have a negative influence on performance (efficiency and degradation) of BAM as a lighting phosphor. The luminescence efficiency and stability are strongly influenced by the formation of Eu³⁺ and a deeper trap during annealing in air. Subsequent annealing in a reducing atmosphere restores the original properties.     

Eu2+,Mn2+在BaZnP2O7中的发光及Eu2+→Mn2+能量传递

采用高温固相法合成了BaZnP₂O₇:Eu²⁺,Mn²⁺荧光粉,并对其发光性质及Eu²⁺对Mn²⁺的能量传递机理进行了研究.Eu²⁺和Mn²⁺在380 nm和670nm的发射峰分别由Eu²⁺的5d—4f跃迁和Mn²⁺的⁴T₁(^{4关键词： 磷酸盐 2+}')" href="#">Eu²⁺ 2+')" href="#">Mn²⁺ 能量传递     

Eu2+,Mn2+在BaZnP2O7中的发光及Eu2+→Mn2+能量传递

采用高温固相法合成了BaZnP₂O₇:Eu²⁺,Mn²⁺荧光粉，并对其发光性质及Eu²⁺对Mn²⁺的能量传递机理进行了研究.Eu²⁺和Mn²⁺在380 nm和670nm的发射峰分别由Eu²⁺的5d—4f跃迁和Mn²⁺的⁴T₁(^{4相似文献}   

Studies on the spin Hamiltonian parameters for Mn2+ in the ZnS nanocrystals and bulks

The spin Hamiltonian parameters (zero-field splitting D, g factors and hyperfine structure constants) are theoretically studied for Mn²⁺ in the ZnS nanocrystals and bulks from the perturbation formulae of these quantities for trigonal and cubic tetrahedral 3d⁵ clusters, respectively. The trigonal Mn²⁺ centre in the ZnS nanocrystals is attributed to the impurity–ligand bond angle related to the C₃ axis about 0.39° larger than that (≈109.47°) of an ideal tetrahedron. Almost the same g factors and hyperfine structure constants for the nanocrystals and bulks can be ascribed to similar crystal-field environments (i.e. comparable cubic field parameters Dq), nearly the same covalency (i.e. the equal covalency factors N) and the Mn²⁺ 3d–3s orbital admixture (i.e. the identical core polarisation constants κ) in both systems. The ligand orbital and spin–orbit coupling contributions are found to be important and should be included in the electron paramagnetic resonance analysis in view of significant covalency.     

Mechanism of relaxation enhancement of spin labels in membranes by paramagnetic ion salts: dependence on 3d and 4f ions and on the anions

Progressive saturation EPR measurements and EPR linewidth determinations have been performed on spin-labeled lipids in fluid phospholipid bilayer membranes to elucidate the mechanisms of relaxation enhancement by different paramagnetic ion salts. Such paramagnetic relaxation agents are widely used for structural EPR studies in biological systems, particularly with membranes. Metal ions of the 3d and 4f series were used as their chloride, sulfate, and perchlorate salts. For a given anion, the efficiency of relaxation enhancement is in the order Mn(2+) > or = Cu(2+) > Ni(2+) > Co(2+) approximately Dy(3+). A pronounced dependence of the paramagnetic relaxation enhancement on the anion is found in the order ClO(-)(4) > Cl(-) > SO(2-)(4). This is in the order of the octanol partition coefficients multiplied by spin exchange rate constants that were determined for the different paramagnetic salts in methanol. Detailed studies coupled with theoretical estimates reveal that, for the chlorides and perchlorates of Ni(2+) (and Co(2+)), the relaxation enhancements are dominated by Heisenberg spin exchange interactions with paramagnetic ions dissolved in fluid membranes. The dependence on membrane composition of the relaxation enhancement by intramembrane Heisenberg exchange indicates that the diffusion of the ions within the membrane takes place via water-filled defects. For the corresponding Cu(2+) salts, additional relaxation enhancements arise from dipolar interactions with ions within the membrane. For the case of Mn(2+) salts, static dipolar interactions with paramagnetic ions in the aqueous phase also make a further appreciable contribution to the spin-label relaxation enhancement. On this basis, different paramagnetic agents may be chosen to optimize sensitivity to different structurally correlated interactions. These results therefore will aid further spin-label EPR studies in structural biology.     

Paramagnetic centers in oak and onion extracts

We have used EPR to study oak bark, bulb onion peel, and their aqueous extracts. We have established that their paramagnetic properties are determined by at least four types of paramagnetic centers: semiquinone radicals, Fe³⁺ ions, and two types of Mn²⁺ ions. We have observed that metal ions are extracted by water from the plant raw material without any change in their original coordination environment. The aqueous extracts were subjected to oxidative processes: mild oxidation in the dried state, strong oxidation when stored as solutions. We have shown that when the solutions are stored, the oxidation reaction is catalyzed by the metal ions and is accompanied by formation of semiquinone radicals. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 440–445, May–June, 2009.