This work reports experimental and theoretical first-order rate constants for the reaction of vinyl radical with C(4)H(8) alkenes: 1-butene, 2-butene, and isobutene. The experiments are performed over a temperature range of 300 to 700 K at 100 Torr. Vinyl radicals (H(2)C horizontal lineCH) were generated by laser photolysis of vinyl iodide (C(2)H(3)I) at 266 nm, and time-resolved absorption spe...

As a member of the organo sulfidoboron (RBS) family, the hitherto elusive ethynylsulfidoboron molecule (HCCBS) has been formed via the bimolecular reaction of the boron monosulfide radical (BS) with acetylene (C2H2) under single collision conditions in the gas phase, exploiting the crossed molecular beams technique. The reaction mechanism follows indirect dynamics via a barrierless addition of ...

QCT calculations were performed to study the behavior of energized NH2OH formed by association collision of NH2 radical with OH radical. A potential energy surface that describes the behavior of the title reaction has been constructed by interpolation of ab initio data. H2O, HON, HNO, NH3, O, H2NO, cis or trans-HONH, and H products and two vibrationally energized NH2OH and NH3O adducts were obs...

Methyl vinyl carbonyl oxide is an important intermediate in the reaction of isoprene and ozone and may be responsible for most of the (*)OH formed in isoprene ozonolysis. We use CBS-QB3 calculations and RRKM/master equation simulations to characterize all the pathways leading to the formation of this species, all the interconversions among its four possible conformers, and all of its irreversib...

The reactions of the 4-tolyl radical (C6H4CH3) and of the D7-4-tolyl radical (C6D4CD3) with 1,2-butadiene (C4H6) have been probed in crossed molecular beams under single collision conditions at a collision energy of about 54 kJ mol(-1) and studied theoretically using ab initio G3(MP2,CC)//B3LYP/6-311G** and statistical RRKM calculations. The results show that the reaction proceeds via indirect ...

We exploited crossed molecular beams techniques and electronic structure calculations to provide compelling evidence that the vinylsulfidoboron molecule (C2H3(11)B(32)S) - the simplest member of hitherto elusive olefinic organo-sulfidoboron molecules (RBS) - can be formed via the gas phase reaction of boron monosulfide ((11)B(32)S) with ethylene (C2H4) under single collision conditions. The rea...

Quantum yields for photochemical ring opening of six alkylcyclobutenes have been measured in hexane solution using 228-nm excitation, which selectively populates the lowest pi,R(3s) excited singlet states of these molecules and has been shown previously to lead to ring opening with clean conrotatory stereochemistry. The compounds studied in this work-1,2-dimethylcyclobutene (1), cis- and trans-...

Ab initio calculations of the potential energy surface for the C3(1Sigmag+)+C2H2(1Sigmag+) reaction have been performed at the RCCSD(T)/cc-pVQZ//B3LYP/6-311G(d,p) + ZPE[B3LYP/6-311G(d,p)] level with extrapolation to the complete basis set limit for key intermediates and products. These calculations have been followed by statistical calculations of reaction rate constants and product branching r...