Peroxides of higher aliphatic ethers

The oxidation of higher aliphatic ethers with oxygen at 50° yields two peroxides as the main oxidation products for each ether, namely a dihydroperoxy-dialkyl ether and a dihydroperoxy-dialkyl peroxide. The mass spectra of these compounds are recorded and the main fragmentation pattern is discussed.     

Geochemical investigation of alluvial sediments: validation of ICP-OES determination of heavy metals. A case study from the Utrata River Valley (central Poland)

The development and validation of a reliable analytical procedure for the determination of selected metals (Cd, Cr, Cu, Pb, Zn and Mn) in sediments accumulated in the Utrata River (Poland) is described. The aqua regia extraction followed by inductively coupled plasma optical emission spectrometry (ICP-OES) was used for this purpose. The optimized analytical procedure was validated, and adequate quality control actions were implemented in order to provide reliable data. The precision under’ within-laboratory’ reproducibility conditions was estimated from duplicate analysis. Certified reference material (CRM) was used in order to evaluate the accuracy of the results regarding the sewage sludge amended soil CRM 143R. The detection limits for all elements of interest were well-below their content in the investigated sediment samples. The obtained reliable data could be used for assessment of the relationship between human economic activity in the past and the geochemical features of the sediments.     

Resonant inelastic x-ray scattering at the limit of subfemtosecond natural lifetime

We present measurements of the resonant inelastic x-ray scattering (RIXS) spectra of the CH(3)I molecule in the hard-x-ray region near the iodine L(2) and L(3) absorption edges. We show that dispersive RIXS spectral features that were recognized as a fingerprint of dissociative molecular states can be interpreted in terms of ultrashort natural lifetime of ～200 attoseconds in the case of the iodine L-shell core-hole. Our results demonstrate the capacity of the RIXS technique to reveal subtle dynamical effects in molecules with sensitivity to nuclear rearrangement on a subfemtosecond time scale.     

Diagram,valence-to-core,and hypersatellite Kβ X-ray transitions in metallic chromium

We report on measurements of the Kβ diagram, valence-to-core (VtC), and hypersatellite X-ray spectra induced in metallic Cr by photon single and double K-shell ionization. The experiment was carried out at the Stanford Synchrotron Radiation Lightsource using the seven-crystal Johann-type hard X-ray spectrometer of the beamline 6-2. For the Kβ diagram and VtC transitions, the present study confirms the line shape features observed in previous works, whereas the K^hβ hypersatellite transition was found to exhibit a complex spectral line shape and a characteristic low-energy shoulder. The energy shift of the hypersatellite relative to the parent diagram line was deduced from the measurements and compared with the result of extensive multiconfiguration Dirac–Fock (MCDF) calculations. A very good agreement between experiment and theory was found. The MCDF calculations were also used to compute the theoretical line shape of the hypersatellite. A satisfactory agreement was obtained between the overall shapes of the experimental and theoretical spectra, but deviations were observed on the low- and high-energy flanks of the hypersatellite line. The discrepancies were explained by chemical effects, which were not considered in the MCDF calculations performed for isolated atoms.     

Depth profiles of Al impurities implanted in Si wafers determined by means of the high-resolution grazing emission X-ray fluorescence technique

The synchrotron radiation based high-resolution grazing emission X-ray fluorescence (GEXRF) technique was used to extract the distribution of Al ions implanted with a dose of 10¹⁶ atoms/cm² in Si wafers with energies ranging between 1 and 100 keV. The depth distributions of the implanted ions were deduced from the measured angular profiles of the Al-Kα X-ray fluorescence line with nanometer-scale precision. The experimental results were compared to theoretical predictions of the depth distributions resulting from ion implantation. A good agreement between experiment and theory was found which proved that the presented high-resolution grazing emission X-ray fluorescence technique is well suited to perform depth profiling measurements of impurities located within the extinction depth, provided the overall shape of the distribution can be assumed a priori.     

Depth profiling of dopants implanted in Si using the synchrotron radiation based high‐resolution grazing emission technique

We report on the surface‐sensitive grazing emission X‐ray fluorescence technique combined with synchrotron radiation excitation and high‐resolution detection to realize depth‐profile measurements of Al‐implanted Si wafers. The principles of grazing emission measurements as well as the benefits offered by synchrotron sources and wavelength‐dispersive detection setups are presented. It is shown that the depth distribution of implanted ions can be extracted from the dependence of the X‐ray fluorescence intensity on the grazing emission angle with nanometer‐scale precision provided that an analytical function describing the shape of the depth distribution is assumed beforehand. If no a priori assumption is made, except a bell shaped form for the dopant distribution, the profile derived from the measured angular distribution is found to reproduce quite satisfactorily the depth distribution of the implanted ions. Copyright © 2012 John Wiley & Sons, Ltd.     

Double K-shell photoionization of low-Z atoms and He-like ions

We report on the investigation of the photon energy dependence of double 1s photoionization of light atoms and compare the cross sections for hollow atom and He-like ion production. Measurements of the Kα hypersatellite x-ray spectra of Mg, Al, and Si were carried out using the Fribourg high-resolution x-ray spectrometer installed at the ID21 and ID26 beam lines at the ESRF. The double-to-single photoionization cross section ratios were derived as a function of the incident photon beam energy and compared to convergent close-coupling (CCC) calculations for He-like ions. The dynamical electron-electron scattering contribution to the DPI cross-sections was found to be more important for neutral atoms than for the He isoelectronic series.     

Crossover and valence band Kβ X-rays of chromium oxides

Kβ X-ray spectra of chromium metal and selected chromium oxides were measured twice using medium resolution flat crystal spectrometer and high resolution spectrometer employing Johansson geometry after excitation with 2 MeV proton beams. The positions and intensities of crossover (Kβ″) and valence (Kβ_2,5) band X-rays relative to the primary Kβ X-ray components were extracted in a consistent way. The results were compared with the existing data obtained by proton and photon induced ionization mechanisms and theoretical predictions. The obtained results in peak relative positions and intensities were analyzed in order to study dependence on the chromium oxidation states and chromium-oxygen bond lengths in selected chromium oxides. Our results obtained by both spectrometers confirm that the linear trend observed for the valence peak relative energy shift as a function of chromium oxidation number does not depend on the experimental resolution. Experimental results for normalized intensities (i.e. relative intensities divided with the number of chromium-oxygen pairs) of crossover and valence band X-rays obtained by both spectrometers are in very good agreement, and follow exponential relationship with the average Cr―O bond lengths in corresponding chromium oxides. The observed trends in crossover and valence X-rays normalized intensities could be used to measure the average chromium-oxygen bond length in various chromium oxides, with the sum of both crossover and valence X-ray normalized intensities being the most sensitive measure.     

The base-catalysed cyclisation of phenyl N-(2-hydroxybenzyl)-N-methylcarbamates is concerted

The kinetics of the cyclisation in aqueous solution of phenyl-(2-hydroxybenzyl)-N-methylcarbamates to 3-methyl- 3,4-dihydrobenzo[e][1,3]oxazin-2-ones and phenolate ions fit the rate law: kobs = kc/(1 + [H3O+]/Ka) The values of kc and pKa fit Br?nsted equations against the pKa's of the corresponding free phenols but the system does not conform to the reactivity-selectivity hypothesis. The values of the Br?nsted parameters beta Y and beta X vary as a function of Y and X according to the equations: beta X = -0.179pKaHY + 0.87 beta Y = -0.179pKaHX + 2.30 The magnitude and sign of the Cordes-Thornton cross-interaction coefficient pXY (-0.179) rule out a stepwise mechanism involving a tetrahedral intermediate and is consistent with a concerted displacement mechanism. A similar concerted mechanism is proposed for the base-catalysed cyclisation of phenyl-N-(2-hydroxyphenyl)-N-methylcarbamate esters to benzoxazol-2-ones.