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.     

Oxydations par le carbonate d'argent sur celite—VII : Oxydations de diols

The oxidation of several secondary-tertiary α diols by silver carbonate on Celite is described. In the steroid series, a 17α,20α diol leads to the related ketol, whereas its 17α,20β isomer is either not affected by the reagent, or slowly cleaved to give a 17-keto steroid.     

Isokinetic Relationships in Alcohol Oxidation with Chromic Acid

The activation parameters for the oxidation of 13 secondary alcohols with chromic acid have been determined. Application of a statistical treatment of Exner [9] shows that the reactions are isoentropic with an average entropy of activation (ΔS^≠) of ?24.0 e. u.     

Erratum

Peculiar transitions in the optical spectra of Mn atoms isolated in argon matrices confirm the existence of Mn₂ molecule. The temperature variation of the absorption and MCD intensity in the range 13-27 K demonstrate that the Mn₂ molecule is antiferromagnetic and allows a precise determination of its ground-state exchange energy: J = ?10.3 ± 0.6 cm^?1.