Barrierless reactions between two closed-shell molecules. I. Dynamics of F(2)+CH(3)SCH(3) reaction

A detailed experimental and theoretical investigation of the first-reported barrierless reaction between two closed-shell molecules [J. Chem. Phys. 127, 101101 (2007)] is presented. The translational energy and angular distributions of two product channels, HF+CH(2)SFCH(3) and F+CH(3)SFCH(3), determined at several collision energies, have been analyzed to reveal the dynamics of the studied reaction. Detailed analysis of the experimental and computational results supports the proposed reaction mechanism involving a short-lived F-F-S(CH(3))(2) intermediate, which can be formed without any activation energy. Other possible reaction mechanisms have been discriminated. The decay of the intermediate and competition between the two product channels have been discussed.     

Dynamics of the F2+CH3SCH3 reaction: a molecule-molecule reaction without entrance barrier

The F(2)+CH(3)SCH(3) reaction was studied with crossed molecular beam techniques and high level ab initio calculations. Significant reactivity was observed even at low collision energies, consistent with the negligible barrier height obtained from the ab initio calculations. All experimental findings are consistent with a weakly bound reaction intermediate of F-F-S(CH(3))(2) structure, which possesses a special type of three-center four-electron bonding. Analogous intermediates can also explain the reactions of F(2) with CH(3)SH and CH(3)SSCH(3).     

Comparison of geometric, electronic, and vibrational properties for isomers of small fullerenes C20-C36

We employ the self-consistent-charge density-functional tight-binding (SCC-DFTB) method for computing geometric, electronic, and vibrational properties for various topological isomers of small fullerenes. We consider all 35 five- and six-member rings containing isomers of small fullerenes, C20, C24, C26, C28, C30, C32, C34, and C36, as first part of a larger effort to catalog CC distance distributions, valence CCC angle distributions, electronic densities of states (DOSs), vibrational densities of states (VDOSs), and infrared (IR) and Raman spectra for fullerenes C20-C180. Common features among the fullerenes are identified and properties characteristic for each specific fullerene isomer are discussed.     

Investigation of the stereochemistry of intermolecular conjugate additions of nucleophiles to acyclic nitrosoalkenes

Michael-type conjugate additions of γ-chiral aldehyde-derived acyclic nitrosoalkenes have been explored using a series of carbon and hetero nucleophiles. In all cases examined, these reactions are stereoselective, leading exclusively to the anti products.     

Synthetic routes towards tetrazolium and triazolium dinitromethylides

Tetrazolium-5-dinitromethylide sodium salt has been prepared (91%) by cyclization of 1-amino-1-hydrazino-2,2-dinitroethene with nitrous acid in water. 5-Imino-1-(hydroxyiminonitromethyl) derivatives were obtained by nitration of 2-(5-amino-1,3-dimethyl-1H-1,2,4-triazol-4-ium-4-yl)- and 2-(5-amino-4-methyl-1H-tetrazolium-1-yl)acetate complex salts. Treatment of 4-methyl-1-(2-oxopropyl)-1-tetrazolium methylsulfate with nitric and sulfuric acid gave methyl (3-nitro-1,2,4-oxadiazol-5-yl)amine (27%) probably via dinitromethylide followed by cyclization and loss of nitrogen.__________Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 127–134, January, 2005.     

Measurement of various decay modes of charmed particlesD 0,D +,D s + andΛ s c

In the CERN NA 32 experiment a high-resolution silicon vertex detector and a purely topological approach have been used to investigate various decays of charmed particles. We observe ～620 fully reconstructed decays ofD ⁰ in 12 channels and determine the branching ratios. For fourD ⁰ decay modes involving a single (unseen) π⁰ the small and narrowD ^*+?D ⁰ mass difference is used to measure their branching ratios. We also observe ～280 fully reconstructedD ⁺ decays in 10 channels, ～90D _s ⁺ decays in 11 channels as well as 160Λ _s ^c and 18 decay channels ofD ⁺. For theD _s ⁺ , we measure the branching fractions within a subset of 16 three- and five-prong decay channels. For theΛ _s ^c , we determine the branching fractions within a sample of 11 three- and five-prong decay channels, nearly all involving a proton.     

Measurement of the masses and lifetimes of the charmed mesonsD 0,D + andD s +

We present the final results on the measurement of the masses and lifetimes of the mesonsD ⁰,D ⁺ andD _s ⁺ in the NA32 experiment at the CERN SPS, using silicon microstrip detectors and charge-coupled devices for vertex reconstruction. We measure the following lifetimes: \(\tau _{D^0 } = 3.88 \pm _{0.21}^{0.23} \cdot 10^{ - 13} s\) using a sample of 479D°→K ^?π⁺π^?π⁺ and 162D°→K ^?π⁺ decays; \(\tau _{D^ + } = 10.5 \pm _{0.72}^{0.77} \cdot 10^{ - 13} s\) with a sample of 317D ⁺→K ^?π⁺π⁺ decays; \(\tau _{D_s^ + } = 4.69 \pm _{0.86}^{1.02} \cdot 10^{ - 13} s\) with a sample of 54D _s ⁺ →K ⁺ K ^?π⁺ decays. We measure the following masses:m _D ⁰=1864.6±0.3±1.0 MeV,m _D ⁺=1870.0±0.5±1.0 MeV and \(m_{D_s^ + } \) =1967.0±1.0±1.0 MeV.