Magnetic resonance studies of the properties of water in cellulose acetate membranes

The properties of water in various cellulose acetate (CA) membranes have been investigated by magnetic resonance techniques. It has been observed that the longitudinal (T₁) relaxation time of ¹⁷O in CA membranes containing H₂ ¹⁷O is considerably shorter (by a factor of 5 to 6) than the corresponding value in pure water. The T₁ values of ²³Na ions contained in these membranes were, however, shorter than the corresponding values observed in measurements of the aqueous mother solution by a factor smaller than 2. The EPR spectra of Mn²⁺ and of Cr³⁺ contained in CA membranes were practically identical to the spectra of the pure aqueous solution.

The data suggest the existence, in the CA membrane, of two “types” of water; a small fraction of highly immobilized “bound” water and the remaining large fraction of “free” water displaying properties almost identical to those of pure bulk water. This model is supported by measurements of the longitudinal relaxation rates of H₂ ¹⁷O in CA membranes which were gradually dehydrated from their water.     

Radiationless intermolecular energy transfer with participation of acceptor excited triplet states

Radiationless energy transfer between like and unlike molecules has been experimentally studied under conditions where acceptor molecules have been excited to the triplet state Homogeneous singlet-triplet-triplet migration has been discovered in highlyconcentrated chlorophyll “a” and pheophytin “a” solutions in castor oil at 183 K by measuring the variation of pigment relative quantum yields of fluorescence and triplet state formation as a function of exciting pulse intensity. Heterogeneous single-triplet-triplet energy transfer has been observed in solid solutions of different complex organic molecules (perylene + phenanthrene, Na-fluorescein+chlorophyll “a”, pyrene+Mg-phthalocyanine) as the fluorescent donor state quenching in the presence of acceptor triplet-excited molecules. Primary emphasis is placed on a direct observation of the effect of energy transfer on the excited-state lifetime of the donor. The benzophenone phosphorescence quenching (shortening of phosphorescence lifetime) in the presence of Mg-mesoporphyrin triplet molecules has been found to be caused by the heterogeneous triplet-triplet-triplet energy transfer. Good agreement of the theoretical and experimental results permits us to conclude that all types of observed transfer processes are described by the Förster-Galanin theory for dipole-dipole radiationless energy transfer with no additional assumptions.     

A Rhodamine Derivative Based Chemosensor with High Selectivity and Quick Respond to Cr<Superscript>3+</Superscript> in Aqueous Solution

In this paper, a new kind of colorimetric chemsensor aiming at detecting Cr³⁺ has been synthesized, and it is based on the “Off-On” effect of a rhodamine derivative. Comparing with other metal irons (Na⁺, K⁺, Ni²⁺, Hg²⁺, Fe³⁺, Mn²⁺, Co²⁺, Cd²⁺, Cu²⁺, Pb²⁺, Zn²⁺, Mg²⁺, Ba²⁺, Ag⁺, Fe²⁺, Ce³⁺), the chemsensor has a quick and accurate response to Cr³⁺ in H₂O-EtOH solution (4/1, v/v). There is an obvious change in color, from colorless to bright pink when Cr³⁺ is detected. According to the fitting curve based on Benesi-Hildebrand equation and working curve of absorption strength in UV-vis spectrum, the binding pattern of Cr³⁺ and the rhodamine derivative follows a 1:1 stoichiometry. The chemsensor shows great potential in monitoring Cr³⁺ in the aqueous medium with high efficiency, which is supposed to complete the recognition in the minimum as 5.2?×?10^?7 mol/L within 5 min.     

Inelastic scattering and radiative capture of protons by Cr50 and Cr54

Total yields and angular distributions of gamma rays following the inelastic scattering of protons from Cr⁵⁰ and Cr⁵⁴ have been measured at proton energies below 2.5 MeV. Gamma ray spectra resulting from the proton radiative capture by Cr⁵⁰ and Cr⁵⁴ were obtained. Transitions from most of the Mn⁵¹ and Mn⁵⁵ low-lying levels have been observed. The experimental results are in good agreement with predictions of the statistical compound nucleus theory.     

CsLiSO4/NH4LiSO4 system investigated by EPR

The single crystals of CsLiSO₄ and the solid solutions Cs _x (NH₄)_{(1? x )}LiSO₄ have been investigated using the EPR technique. Two kinds of vanadyl doped samples were considered – as-grown from the aqueous solutions of appropriate compounds and after a thermal treatment. It has been established that in as-grown crystals the EPR spectra of vanadyl ions were very complex due to the presence of more than one paramagnetic site in the lattice. At least two such sites were identified and spin Hamiltonian parameters were calculated for all the sites. After annealing the crystals at about 400?K, a significant decrease in the intensities of the EPR lines of VO²⁺ complexes was observed. In well-annealed samples the complexity of the EPR spectra has been found to disappear. Additionally, the third kind of vanadyl complexes were created during this treatment. It has also been shown that the EPR spectra of Cr³⁺ ions in CsLiSO₄ could be observed without any additional sample treatment reported in literature like an irradiation or thermal decomposition. It was established that the VO²⁺ and Cr³⁺, being sensitive to structural phase transition in the CsLiSO₄, can be used as a probe for the structural changes in the CsLiSO₄/NH₄LiSO₄ system.     

The size of the proton

The root-mean-square (rms) charge radius r _p of the proton has so far been known only with a surprisingly low precision of about 1% from both electron scattering and precision spectroscopy of hydrogen. We have recently determined r _p by means of laser spectroscopy of the Lamb shift in the exotic “muonic hydrogen” atom. Here, the muon, which is the 200 times heavier cousin of the electron, orbits the proton with a 200 times smaller Bohr radius. This enhances the sensitivity to the proton’s finite size tremendously. Our new value r _p?=?0.84184 (67) fm is ten times more precise than the generally accepted CODATA-value, but it differs by 5 standard deviations from it. A lively discussion about possible solutions to the “proton size puzzle” has started. Our measurement, together with precise measurements of the 1S–2S transition in regular hydrogen and deuterium, also yields improved values of the Rydberg constant, R _?∞??=?10,973,731.568160 (16) m^???1.     

Flat coordinates of topological conformal field theory and solutions of the Gauss–Manin system

A luminescent trace has been observed in a ruby crystal (Al₂O₃: Cr³⁺) that rotates at a frequency of 2 to 200 Hz and is irradiated by 532-nm coherent electromagnetic radiation. A method has been proposed to determine the lifetime of the excited electronic state of chromium ions from the measurement of the length of an arc of the trajectory of a light spot on the surface of a rotating ruby single crystal. A “comet trace” formed at the passage of radiation through the rotating crystal near the absorption band of the material has been detected inside the ruby crystal. It has been shown that the theory based on the analysis of the motion of polaritons in the rotating reference frame is in satisfactory agreement with experimental results.     

Photostimulated electron transfer and its action on paramagnetism of Sp<Subscript>3</Subscript>Cr(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript> single crystals

The effect of irradiation by ultraviolet light on the effective magnetic moment of a paramagnetic single crystal based on photochrome spiropyran (Sp) and chromium oxalates Sp₃Cr(C₂O₄)₃ molecules is detected. It is shown that the deviation of the temperature dependence of the magnetic moment from the Curie law is caused not by the exchange interaction, but by electron redistribution between Cr³⁺ and Cr⁴⁺ ions and spiropyran molecules Sp⁰ and Sp⁺. Analysis of the angular dependence of EPR spectra makes it possible to determine the contribution of Cr³⁺ ions to the magnetic properties of the crystals and to determine the crystal field parameters D = 0.619 cm⁻¹ and E = 0.024 cm⁻¹. Irradiation of hydrated samples by ultraviolet light leads to intensity redistribution of EPR lines attributed to Cr³⁺ and Sp⁰. Thermally stimulated paramagnetism of triplet states of spiropyran ions Sp⁺ and the SpI salt is observed.     

KZnF3:Cr3+和KMgF3:Cr3+四角对称电子顺磁共振参量与晶格缺陷的研究

用Newman叠加模型研究了KZnF₃:Cr³⁺四角对称基态的零场分裂,证实了Zn²⁺空位和畸变的存在;并指出,空位对晶场的贡献不可忽略。计算得到:KZnF₃:cr³⁺晶体[0,01]方向的一个F^-配体向Cr³⁺移动Δ(KZnF₃)=0.0029-0.0043nm。还研究了KMgF₃:Cr^{3+关键词：}     

Electron spin resonance of chromia-yttria solid solutions

Electron spin resonance spectra of chromia-yttria solid solutions have been studied at room temperature for Cr concentrations between 0.20 and 2.00 mol%. Isolated Cr³⁺ ions in sites with two different symmetries were observed, as well as well as Cr³⁺ ions coupled by the exchange interaction. The relative concentration of isolated to coupled Cr³⁺ ions decreases with increasing chromium concentration. The results are consistent with the assumption that the chromium ions occupy preferentially the C₂ symmetry sites. A theoretical calculation based on this model yields an effective range of the exchange interaction between Cr³⁺ ions of 0.64 nm, of the same order as that of Cr³⁺ ions in MgO.     

Electronic absorption spectrum of Cr3+ in calcium formate single crystals

Optical absorption spectra of Cr³⁺ ions in calcium formate single crystals with two different dopants have been studied at room and liquid nitrogen temperatures. The observed spectra have been attributed to Cr³⁺ ions in octahedral environment with tetragonal distortion. The values of the crystal field and Racah parameters have been evaluated.     

Optical spectra and energy levels of the Cr ions in MWO4 (M=Mg, Zn, Cd) and MgMoO4 crystals

Single crystals of MWO₄ (M=Mg, Zn, Cd) and MgMoO₄ doped with Cr³⁺ have been grown by the flux growth method. Their optical spectra have been systematically measured and assigned on the basis of the classical Ligand Field Theory. The exchange charge model of the crystal field has then been applied to calculate the crystal field parameters (CFPs) and the energy levels of the Cr³⁺ ion in all studied crystals. These are in reasonable agreement with the experimental data. Systematic trends in the CFPs values, crystal field splittings and Racah parameters have been evidenced and their relation with sizes and symmetry properties of the host cavities occupied by Cr³⁺ has been pointed out.     

Using the Mössbauer spectroscopy of <Superscript>121</Superscript>Sb nuclei to differentiate the effects of Cr and Sb co-dopants on the photocatalytic activity of anatase-type polycrystalline TiO<Subscript>2</Subscript> powders

The rates of the photocatalytic decolorization of methyl orange solutions in the presence of anatase powders modified by Cr³⁺ and Sb⁵⁺ co-dopants are compared with allowance for data on the actual valence state of antimony in the catalyst, obtained using ¹²¹Sb Mössbauer spectroscopy. The reported results point to the catalytic activity of the Cr⁶⁺ ions formed to compensate for the Cr³⁺ charge deficit in antimony-free samples.     

Sensing behaviour of tin doped chromium oxide gas sensor toward ethanol

In this paper, the enhancement of gas sensing response due to addition of tin into Cr₂O₃ has been reported. Sn-doped Cr₂O₃ nanoparticles have been prepared by a co-precipitation method and characterised by X-ray diffraction, field emission scanning electron microscopy and energy dispersive X-ray analysis. X-ray diffraction studies revealed the substitution of Cr³⁺ ions by Sn⁴⁺ ions. Field emission scanning electron microscopy images exhibited presence of clusters and agglomerates on the surface. The concentration of tin, used as dopant, was varied from 1 to 5?wt.% and its effect on gas sensing response has been studied. Synthesised powders were applied as thick film onto alumina substrate and tested for ethanol sensing at different operating temperatures and all the sensors gave an optimum response at 250?^°C. The activation energy of conduction for all the samples was estimated using Arrhenius plots and it was observed that the sample doped with 4?wt.% Sn possesses minimum activation energy, and interestingly this sample gave the best sensing response in the lot.     

Cr<Superscript>3+</Superscript> spectroscopy study in ZnO-codoped and Zn-in-diffused congruent LiNbO<Subscript>3</Subscript>:Cr crystals

This paper reports on the spectroscopy properties, absorption and luminescence, of Cr³⁺ ions in singly doped, ZnO-codoped, and Zn in-diffused LiNbO₃:Cr crystals. In addition to the broad absorption, inter-ionic transitions ascribed to Cr³⁺ ions located in Li⁺ and Nb⁵⁺ sites; [Cr]_Li and [Cr]_Nb centres two absorption bands at higher energy are reported and ascribed to the charge transfer transitions of the Cr³⁺ ions of the two defect centres. The charge transfer transitions are used as optical probe to study the role of the Zn ions in the Zn in-diffused LiNbO₃:Cr samples. It has been observed that the Zn-in-diffused processes created [Cr]_Nb centres in the diffusion zone. The location of the diffused Zn²⁺ ions is considered to be in Li⁺ site, displacing the Cr³⁺ ions from the Li⁺ sites, [Cr]_Li, to the Nb⁵⁺ positions, [Cr]_Nb.     

The luminescence of Fe3+ and Cr3+ IN α-gallia

The photoluminescence of Fe³⁺ in octahedral oxygen co-ordination has been observed in Fe³⁺- doped α-gallia. The energy of the emission is in good agreement with that predicted from measured spectral data for Cr³⁺ in α-gallia and the literature data for Cr³⁺ and Fe³⁺ in α-alumina.     

Influence of the surface electric field in ion-beam-surface interaction at grazing incidence

We have measured the polarization of light emitted after ion surface scattering at small angle of incidence. The measurements are carried out with H⁺-, H ₂ ⁺ - and He⁺-ions under UHV-conditions with mono- and polycrystalline targets. We explain the typical variation of the polarization as “post collision Stark interaction” (PCSI) in the surface electric field, which can force transitions between nearly degenerate terms. The electric field is composed of two different contributions, a strong but short range surface field which is “seen” by atomsand ions and a long range but weak field due to the image charge which is “seen” to first orderonly by ions. The influence of the electric field on H-Balmer radiation is negligible at typical survival distances r_s≧0.35nm. But in contrast to H-atoms He⁺-ions feel the additional influence of the image field leading to a strong alteration of the polarization of the emitted light. The polarization of the Balmer-radiation stemming from Coulomb exploding H ₂ ⁺ -beams is observed to be modified by the electric field of the “spectator proton”.     

Measurement of the proton NMR field shift in aqueous solutions containing Cu2+, Cr3+, Fe3+ and Mn2+ ions

There are presented measurements of the NMR field shifts for aqueous protons in aqueous solutions containing paramagnetic inorganic compounds of Cu²⁺, Cr³⁺, Fe³⁺ and Mn²⁺ ions. The measurements have been performed on samples in the form of transversally magnetized long cylinders using both the internal and external NMR standards. The experimentally determined shifts are related to the NMR field position of protons in pure water. The results for demagnetizing shifts are compared with the data which were computed from the magnetic susceptibility values (measured by magnetostatic method), the chemical shifts are compared with the results of other authors. Results of measurements indicate a small chemical shift of internal standards in some solutions.     

Effect of external electric field on R line absorption spectra in LiNbO3:Cr3+ crystals

The effect of an external electric field on the R absorption lines of LiNbO₃:Cr³⁺ crystals has been studied by a high-sensitivity differential technique at 77 K. Linear Stark effect has been observed in a field directed along the trigonal crystal axis. No effect of the field was observed when directed perpendicular to this axis. These characteristics of the Stark effect provide a convincing argument for the electric dipole moments of Cr³⁺ centers being oriented along the trigonal C ₃ axis of the crystal and indicate that the chromium centers in LiNbO₃ have C ₃ symmetry. Fiz. Tverd. Tela (St. Petersburg) 39, 2053–2056 (November 1997)     

Magnetic behavior in the incommensurate phase ∼LaCrS3:: effect of the partial substitution of Cr by Ti on the magnetic properties

Dilution of the magnetic interactions between Cr³⁺ ions by Ti³⁺ ions was observed in the CrS₂ layer of the misfit-layer compound ∼LaCrS₃. Pure ∼LaCrS₃ has complex magnetic properties which are reminiscent of spin glass behavior. This magnetic behavior comes from both the modulated character of the structure and the magnetic frustration of the planar-antiferromagnetic-triangular network of Cr³⁺ ions. Thus, there is a large hysteresis between the zero field cooled and the field cooled magnetic susceptibility curves below the transition temperature (≈75 K). Formation of a solid solution ∼LaCr_1−xTi_xS₃ by the addition of Ti³⁺ ions results in the decrease of transition temperature up to a doping level of x≈0.5, where the transition is no longer observed. The magnetic behavior of the phase with x≈0.5 is similar to that of several random exchange antiferromagnetic compounds.