Circular dichroism spectra of langasite family crystals in the range of electronic transitions of structure defects

The absorption and circular dichroism spectra of langasite family crystals are studied. Wide bands in the range of 285–500 nm that are related to the structure lattice defects are found. For all the crystals, these bands are in approximately the same spectral region, have identical structures, and can be attributed to one type of defects formed by cation vacancies and excess oxygen atoms in the optically active positions.     

Thermoluminescence analysis for testing the irradiation of spices

Thermoluminescence signals of irradiated and unirradiated spices and herbs are due to inorganic matter grains adhering to the surfaces. This study reports the mineral composition of this dust being, mainly quartz, calcite and philosilicates; it shows the differences between samples exposed and non-exposed to -radiation on the basis of TL signals after long storage periods (1–16 months). A saturation process in the TL signal is found when the samples absorb doses higher than 5 kGy. Finally, the TL glow curve intensities do not suffer significant changes with the dose rate of the -source used in the radiation process.     

A Screening Method for Polycyclic Aromatic Hydrocarbons Determination in Water by Headspace SPME with GC-FID

A simple method for determination of polycyclic aromatic hydrocarbons (PAHs) in water using headspace solid-phase microextraction (HS-SPME) with gas chromatography-flame ionisation detector (GC-FID) was developed. In order to obtain the convenient experimental conditions for HS-SPME extraction an experimental design with two steps was accomplished. A 2^6-2 fractional factorial design and central composite design (CCD) considering three significant factors were used. Naphthalene, anthracene and fluoranthene were chosen as representatives of two, three and four aromatic rings, and the global response of three PAHs was used for the results, evaluation. The chosen extraction conditions were: 85 μm polyacrylate fibre; 50 °C temperature; 60 min time; 20 mL-dissolution volume (in 40 mL glass vial); without salt addition; and 2 min desorption time. The procedure was extended to other seven PAHs (acenaphthylene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene and benzo(a)anthracene) and the analytical characteristics were checked. The limit of detection (LOD) was from 0.08 (anthracene) to 0.20 μg L^?1 (naphthalene). The precision expressed as relative standard deviation (RSD in %) using 50 μg L^?1 of each analyte ranged from 6.8 to 17 %. The method was applied to the analysis of the surface waters and leaching waters of contaminated soils from Gipuzkoa (North Spain). The PAHs were not detected in surface water samples. Most of the PAHs were found in the leachates from contaminated soils showing a maximum global value of 75.5 μg L^?1.     

Ab initio analytical potential energy surface and quasiclassical trajectory study of the O(+)((4)S)+H(2)(X (1)Sigma(g) (+))-->OH(+)(X (3)Sigma(-))+H((2)S) reaction and isotopic variants

An analytical potential energy surface (PES) representation of the O(+)((4)S)+H(2)(X (1)Sigma(g) (+)) system was developed by fitting around 600 CCSD(T)/cc-pVQZ ab initio points. Rate constant calculations for this reaction and its isotopic variants (D(2) and HD) were performed using the quasiclassical trajectory (QCT) method, obtaining a good agreement with experimental data. Calculations conducted to determine the cross section of the title reaction, considering collision energies (E(T)) below 0.3 eV, also led to good accord with experiments. This PES appears to be suitable for kinetics and dynamics studies. Moreover, the QCT results show that, although the hypotheses of a widely used capture model are not satisfied, the resulting expression for the cross section can be applied within a suitable E(T) interval, due to errors cancellation. This could be a general situation regarding the application of this simple model to ion-molecule processes.     

Ab initio potential energy surface, variational transition state theory, and quasiclassical trajectory studies of the F+CH4-->HF+CH3 reaction

In this work we present a study of the F+CH(4)-->HF+CH(3) reaction (DeltaHdegrees(298 K)=-32.0 kcal mol(-1)) using different methods of the chemical reaction theory. The ground potential energy surface (PES) is characterized using several ab initio methods. Full-dimensional rate constants have been calculated employing the variational transition state theory and using directly ab initio data. A triatomic analytical representation of the ground PES was derived from ab initio points calculated at the second- and fourth-order M?ller-Plesset levels with the 6-311+G(2df,2pd) basis set, assuming the CH(3) fragment to be a 15 a.m.u. pseudoatom in the fitting process. This is suggested from experiments that indicate that the methyl group is uncoupled to the reaction coordinate. A dynamics study by means of the quasiclassical trajectory (QCT) method and employing this analytical surface was also carried out. The experimental data available on the HF internal states distributions are reproduced by the QCT results. Very recent experimental information about the reaction stereodynamics is also borne out by our QCT calculations. Comparisons with the benchmark F+H(2) and analogous Cl+CH(4) reactions are established throughout.     

On Sets that Meet Every Hyperplane in n-Space in at Most n Points

A simple proof that no subset of the plane that meets everyline in precisely two points is an F-set in the plane is presented.It was claimed that this result can be generalized for setsthat meet every line in either one point or two points. No proofof this assertion is known, however. The main results in thispaper form a partial answer to the question of whether the claimis valid. In fact, it is shown that a set that meets every linein the plane in at least one but at most two points must bezero-dimensional, and that if it is -compact then it must bea nowhere dense G-set in the plane. Generalizations for similarsets in higher-dimensional Euclidean spaces are also presented.     

Topological equivalence of discontinuous norms

We show that for everyp>0 there is an autohomeomorphismh of the countable infinite product of linesR ^Nsuch that for everyr>0,h maps the Hilbert cube [−r, r] ^N precisely onto the “elliptic cube” . This means that the supremum norm and, for instance, the Hilbert norm (p=2) are topologically indistinguishable as functions onR ^N.The result is obtained by means of the Bing Shrinking Criterion. Research supported in part by a grant from NSF-EPSCoR Alabama.     

Absorption and Circular Dichroism Spectra of La<Subscript>3</Subscript>Ga<Subscript>5</Subscript>SiO<Subscript>14</Subscript> Crystals Doped with Pr<Superscript>3+</Superscript>, Ho<Superscript>3+</Superscript>, and Er<Superscript>3+</Superscript> Ions

The absorption and circular dichroism (CD) spectra of La₃Ga₅SiO₁₄ langasite crystals doped with Pr³⁺, Ho³⁺, and Er³⁺ ions have been studied in the wavelength range of 350–700 nm. The electronic transitions of these ions, which replace La3+ ions in the 3e position with the symmetry 2, are observed in the spectra. All transitions are active in both the absorption and CD spectra. The dipole strengths D _om, rotational strengths R _om, and anisotropy factors g have been calculated for well-resolved bands. Some features are noted for the spectra that were obtained, and their relationship with the structure disorder is considered