Franck-Condon factors and radiative lifetime of the A2Π(1/2)-X2Σ+ transition of ytterbium monofluoride, YbF

The fluorescence spectrum resulting from laser excitation of the A(2)Π(1/2)←X(2)Σ(+) (0,0) band of ytterbium monofluoride, YbF, has been recorded and analyzed to determine the Franck-Condon factors. The measured values are compared with those predicted from Rydberg-Klein-Rees (RKR) potential energy curves. From the fluorescence decay curve the radiative lifetime of the A(2)Π(1/2) state is measured to be 28 ± 2 ns, and the corresponding transition dipole moment is 4.39 ± 0.16 D. The implications for laser cooling YbF are discussed.     

Electron distribution in partially reduced mixed metal oxide systems: infrared spectroscopy of CemVnOo(+) gas-phase clusters

Vibrational predissociation spectra of rare-gas-tagged [(CeO(2))(VO(2))(1-2)](+) and [(Ce(2)O(3))(VO(2))](+) clusters are measured in the 400-1200 cm(-1) region. Density functional theory (DFT) is used to determine the geometric and electronic structure of low-energy isomers of the partially reduced clusters. Comparison of experimental and simulated spectra provides evidence for the larger stability of Ce(+3)/V(+5) compared to that of Ce(+4)/V(+4), which confirms that the exceptionally high reducibility of Ce(+4) accounts for the promoting role of ceria in supported vanadium oxide catalysts.     

Direct conversion of methane to higher hydrocarbons using AlBr3-HBr superacid catalyst

The direct gas phase catalytic oligomerization of methane at temperatures ≤673 K has been demonstrated using AlBr(3)-HBr superacid. The reaction produces C(2)+ hydrocarbons and hydrogen in a single step at 1 atm in a continuous flow reactor at a nominal residence time of 60 s. The essentially complete conversion of methane appears to be due to protolytic activation of methane in the presence of H(+)AlBr(4)(-).     

Studies on the emission behavior of polypropylene by gas chromatography/mass spectrometry with static headspace or thermodesorption

Emissions from polypropylene (PP) may cause undesired smell, be harmful, or lead to so-called fogging which prohibits its use for car interiors. Thus, qualitative as well as quantitative emission studies are necessary. Thermodesorption (TDS) and static headspace (sHS) with subsequent GC-MS analysis are two powerful tools for analyzing the emission behavior of polymers with a minimum of sample handling. In this work we investigated the emission behavior of PP with TDS and sHS coupled to GC-MS paying special attention to quantitative considerations and to the relevance of emitted substances for fogging phenomena. After extraction for 30min and incubation for 2h, TDS-GC-MS and sHS-GC-MS results were satisfyingly repeatable (with relative standard deviations up to 5%). TDS allowed to introduce substances up to higher boiling points into the GC-MS system, but required to control sample geometry, as emission depended rather on sample surface than on sample mass. In sHS, emission was governed by partitioning between the gas and the sample phase rather than by full evaporation of the analytes. Above a certain analyte-dependent amount, peak area became independent of the sample amount. However, if the sample amount was kept constant, peak areas of emitted substances showed a linear dependence upon concentration of volatiles. Therefore, accurate quantitation was still possible. Typically alkanes, alkenes and dialkenes dominate TDS-GC-MS and sHS-GC-MS chromatograms of PP. They only contributed to fogging if they had a chain length higher than C16. These substances were only detectable when TDS was used for sample introduction, but not with sHS. sHS-GC-MS is thus not useful for judging fogging behavior.     

Four-nucleon system with Δ-isobar excitation

The four-nucleon bound state and scattering below three-body breakup threshold are described based on the realistic coupled-channel potential CD Bonn+Δ$\text{Bonn}+\mathrm{\Delta }$ which allows the excitation of a single nucleon to a Δ isobar. The Coulomb repulsion between protons is included. In the four-nucleon system the two-baryon coupled-channel potential yields effective two-, three- and four-nucleon forces, mediated by the Δ isobar and consistent with each other and with the underlying two-nucleon force. The effect of the four-nucleon force on the studied observables is much smaller than the effect of the three-nucleon force. The inclusion of the Δ isobar is unable to resolve the existing discrepancies with the experimental data.     

Ionization of methane in strong and ultrastrong relativistic fields

The photoionization of methane is reported for intensities up to 10(19) W/cm2 with linear and circular polarized light. While fragmental ions (e.g., CH3+, CH+, C+, C2+) created from 10(14) W/cm2 to 10(15) W/cm2 are formed by Coulomb explosion, ionization to form C3+ and C4+ involves Coulomb explosion and tunneling ionization. In ultrastrong fields, removal of a carbon K-shell electron from methane proceeds via tunneling and rescattering ionization, without the influence of molecular channels. Photoelectrons from methane at 10(19) W/cm2 extend up to kinetic energies of 0.6 MeV.     

Analysis of the interactions in FCCF:(H2O) and FCCF:(H2O)2 complexes through the study of their indirect spin–spin coupling constants

A theoretical study of FCCF:(H₂O)_n complexes, with n?=?1 and 2, has been carried out by means of ab initio computational methods. Three kinds of interactions are observed in the complexes: H···π and H···F hydrogen bonds and O···FC tetrel bonds. The indirect spin–spin coupling constants have been calculated at the CCSD/aug-cc-pVTZ-J computational level. Special attention has been paid to the dependence of the different intramolecular coupling constants in FCCF on the distance between the coupled nuclei and the presence or absence of water molecules. The exceptional sensitivity shown by these coupling constants to the presence of water molecules is quite notorious and can provide information on the bonding structure of the molecule.     

Morphology and Properties of Poly(oxymethylene) Engineering Plastics

Comparative WAXD/SAXS/SEM/DSC structural studies of a series of semi-crystalline poly(oxymethylene) (POM) engineering plastics, including the commercial products, homopolymer Delrin^® and typical poly(oxymethylene-co-oxyethylene)s, and a few lab-made POM compositions, were performed. The latter differed in their content of functional additives (present in low concentrations) and POM molecular weight characteristics. In parallel, their densities, thermal behavior/laser-interferometric creep rate spectra (DSC/CRS) at 20-180 °C, as well as long-term creep resistance (LTCR) at 20 °C were studied. It has been found that introducing the nucleating agents and oxyethylene units resulted in formation of more fine spherulitic or practically non-spherulitic structure with close- or loose-packed lamellar stacks. The presence of both “thick” (5-10 nm) and “thin” (1.5-3 nm) lamellae in the weight ratio of ∼3:1 was shown in all cases. Close values of real POM crystallinities, not exceeding 50%, were obtained by WAXD and DSC. A predominant role of “straightened out” or slightly bent tie chains in disordered layers of isotropic POMs was presumed, resulting in segmental dynamics differently constrained by crystallites (DSC/CRS data). As a result, certain morphology - density - creep resistance correlations were found.     

ChemInform Abstract: Coordination of Cu+ and Cu2+ Ions in ZSM‐5 in the Vicinity of Two Framework Al Atoms.

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