Eu and Sb Mössbauer spectroscopy of EuSbSe3 and EuBiSe3

¹⁵¹Eu and ¹²¹Sb Mössbauer spectroscopy of EuSbSe₃ and EuBiSe₃ were measured at different temperatures. The presence of divalent europium and trivalent antimony were confirmed. The largely negative values of the isomer shift in ¹⁵¹Eu spectrum show highly ionic bonding within these two compounds. Both of them show magnetic hyperfine field splitting at 4.2 K, which indicates a change in the orientation of the EFG principal axis with respect to the magnetic hyperfine field direction. EuSbSe₃ has slightly smaller electron density at the antimony nuclei, compared to Sb₂Se_3.     

Angle-resolved ultraviolet photoemission of pyridine adsorbed on Pd(111)

The valence levels of phridine adsorbed on Ph(111) at room temperature are investigated by angle-resolved UV photoemission using Hel and Hell resonance radiation. The spectra are interpreted in terms of a reduction of the surface molecule symmetry from C_2v to C₈. We suggest that pyridine is adsorbed with its aromatic ring plane tilted wit respect to the surface interaction with the substrate taking place through both N lone-pair and π electrons.     

Half Antiperovskites VI: On the Substitution Effects in Shandites InxSn2–xCo3S2

In the shandite type solid solution In_xSn_2–xCo₃S₂ the transition from half metal ferromagnetic Sn₂Co₃S₂ to the new thermoelectric InSnCo₃S₂ is related to A = In, Sn on different crystallographic sites. Effects and origin of crystal and electronic structure changes induced by A = In are now investigated within the solid solution 0 ≤ x ≤ 2 including In₂Co₃S₂. Effects are studied from X‐ray data, ¹¹⁹Sn Mößbauer spectroscopy, and ab initio calculations. Their origin is explored by DFT modeling on site preference of In and Sn in a supercell, electric field gradients (EFG), spin polarization, band structures, and direct space analyses (ELF, AIM). Indium is found to cause the crystal structure distortion on one A site, the electronic structure distortion to the other, as a consequence of inverted anisotropic bonding.     

A General Strategy for the Catalytic,Highly Enantio‐ and Diastereoselective Synthesis of Indolizidine‐Based Alkaloids

Sixteen indolizidine‐based alkaloids (IBAs) that were isolated as poison constituents of the skin of frogs were synthesized in a highly flexible and stereoselective manner. As a key step, a three‐component, organocatalytic, highly enantio‐ and diastereoselective vinylogous Mukaiyama–Mannich reaction was employed furnishing optically highly enriched butyrolactams as central intermediates on a multigram scale. The attached six‐membered ring was constructed through cyclization of the pendant enoate moiety onto the pyrrolidine ring. The absolute configuration of the bridgehead chiral center and the adjacent 8‐position was established in the initial vinylogous Mannich reaction, whereas the 3‐ and 5‐substituents were introduced through organometallic addition at a late stage of the synthesis with full stereochemical control from the substrate. With this strategy, simple as well as even more complex alkaloids were accessible in good overall yields as single stereoisomers. These syntheses also served to establish the absolute and relative configuration of those IBAs that had never been synthesized before.     

Temperature dependence of sorptive deformation

A study has been made of the temperature dependence of deformation of CaA, CaX, and LaX zeolites when krypton or xenon is adsorbed, and also the deformation of activated carbon when dimethyl ether is adsorbed. It has been shown that the volume compressibility and the standard chemical potential of the adsorbate in a vacancy solution, within the interval of temperatures and pressures that were investigated, can be considered as linear functions of temperature. In this case, knowledge of the temperature dependence of sorptive deformation offers a means for calculating sorptive deformation curves for other temperatures.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Institute of Petrochemical Synthesis, Russian Academy of Sciences. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 23–28, January, 1992.     

Characterization of modified glassy carbon films

The composition and structure of the thin conversion films at pre- and breakdown state are investigated. The breakdown leads to a modified structure and composition. Raman spectra of modified films show the formation of glassy carbon with a defined size of crystallites. A typical morphology characterized by a strong structured surface indicates this breakdown state. Electron diffraction patterns of the pre-breakdown state show the presence of titanium nitride, titanium carbide and titanium oxide.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Adsorption of H2O on Al(111)

The adsorption of H₂O on Al(111) has been studied by ESDIAD (electron stimulated desorption ion angular distributions), LEED (low energy electron diffraction), AES (Auger electron spectroscopy) and thermal desorption in the temperature range 80–700 K. At 80 K, H₂O is adsorbed predominantly in molecular form, and the ESDIAD patterns indicate that bonding occurs through the O atom, with the molecular axis tilted away from the surface normal. Some of the H₂O adsorbed at 80 K on clean Al(111) can be desorbed in molecular form, but a considerable fraction dissociates upon heating into OH_ads and hydrogen, which leaves the surface as H₂. Following adsorption of H₂O onto oxygen-precovered Al(111), additional OH_ads is formed upon heating (perhaps via a hydrogen abstraction reaction), and H₂ desorbs at temperatures considerably higher than that seen for H₂O on clean Al(111). The general behavior of H₂O adsorption on clean and oxygen-precovered Al(111) (θ_O ? monolayer) is rather similar at low temperature, but much higher reactivity for dissociative adsorption of H₂O to form OH _adsis noted on the oxygen-dosed surface around room temperature.