- Ion chemistry in XH4/allene (X = Ge, Si) gaseous mixtures - Formation of X-C bonds
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The gas-phase ion chemistry of germane/allene and silane/allene mixtures has been studied, with the aim of obtaining information on the experimental conditions leading to the formation of clusters of increasing size containing Ge or Si bonded to carbon atoms. Mechanisms of ion/molecule reactions have been elucidated by ion-trap mass spectrometry using single and multiple isolation steps. Rate constants for the most important reactions have been determined experimentally and compared with collisional rate constants. The germane/allene mixtures display a low reactivity and the most abundant germanium and carbon containing ion is GeCH3/+. However, chain propagation proceeds after the first nucleation step, even if rather slowly, with the formation of large clusters such as Ge4C3H3/+ at low abundance. In contrast, the silane/allene mixtures are very reactive and many different processes are observed, with the formation of several silicon and carbon containing ions with appreciable efficiency. Chain propagation proceeds mainly through reactions of silicon-containing ions with allene molecules and the subsequent formation of large clusters such as Si3C3H5/+ and Si4C3H7/+.
- Benzi, Paola,Operti, Lorenza,Rabezzana, Roberto
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p. 505 - 512
(2007/10/03)
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- Ion-Molecule Reactions of CF3+ with Simple Unsaturated Aliphatic Hydrocarbons at Near-Thermal Energy
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Ion-molecule reactions of CF3+ with C2H2, C2H4, and C3H6 have been studied at near-thermal energy (0.05 eV) by using an ion beam apparatus.Initial product ion distributions and reaction rate constants were determined and compared with previous beam and selected ion flow tube (SIFT) data.The CF3+/C2H2 reaction produces exclusively the electrophilic adduct C3H2F3+ ion.For C2H4 and C3H6, hydride abstraction and electrophilic addition followed by HF elimination or fluoride transfer occur in parallel.The branching ratios of the former and latter reactions are 0.29 +/- 0.04:0.71 +/- 0.06 for the CF3+/C2H4 reaction and 0.07 +/- 0.02:0.93 +/- 0.07 for the CF3+/C3H6 reaction.On the basis of theoretical calculations of potential energies for the CF3+/C2H2 and CF3+/C2H4 systems, the lack of the HF elmination channel in the CF3+/C2H2 reaction, whereas the lack of the initial adduct ion in the CF3+/C2H4 reaction, is attributed to the different stability of the intermediate adduct ions for HF elimination.The reaction rate constants were 0.45 x 1E-9, 1.3 x 1E-9, and 1.6 x 1E-9 cm3 s-1 for C2H2, C2H4, and C3H6, respectively, which correspond to 46percent, 120percent, and 130percent of calculated rate constants from Langevin theory or a parametrized trajectory model.Although there are significant discrepancies in the product ion distributions between the present beam experiment and the previous beam data, the product ion distributions and the reaction rate constants obtained here are in reasonable agreement with the previous SIFT data.
- Tsuji, Masaharu,Aizawa, Masato,Nishimura, Yukio
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p. 3195 - 3200
(2007/10/02)
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- Gas-phase measurements of the kinetics of BF2(+)-induced polymerization of olefinic monomers
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The initial steps in the BF2(+)-induced polymerization of the monomers of ethylene, propylene, cis-2-butene, isobutene, and styrene have been observed in the gas phase at room temperature using the Selected-Ion Flow Tube (SIFT) technique.Rate constants and product distributions have been determined for the initiation of the polymerization in each case.All five initiation reactions were found to be rapid (k >/= 5.0*10-10 cm3 molecule-1 s-1).The primary product ions that propagate polymerization have been identified and sequential addition reactions have been followed in all five systems.For ethylene the energetics of the initial steps have been followed using ab initio molecular orbital theory.Reaction of BF2+ with the vapours of water and benzene have also been characterized. Key words: ion-induced polymerization; alkenes; kinetics; gas phase ion chemistry
- Forte, Leonard,Lien, Min H.,Hopkinson, Alan C.,Bohme, Diethard K.
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p. 1576 - 1583
(2007/10/02)
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- Selected-ion flow tube studies of reactions of the radical cation (HC3N)+. in the interstellar chemical synthesis of cyanoacetylene
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The radical cation (HC3N)+. was produced in a Selcted-Ion Flow Tube (SIFT) apparatus from cyanoacetylene by electron impact and reacted at room temperature in helium buffer gas with a selection of molecules including H2, CO, HCN, CH4, H2O, O2, HC3N, C2H2, OCS, C2H4, and C4H2.The observed reactions exhibited a wide range of reactivity and a variety of pathways including charge transfer, hydrogen atom transfer, proton transfer, and association.Association reactions were observed with CO, O2, HCH and HC3N.With the latter two molecules association was observed to proceed close to the collision limit, which is suggestive of covalent bond formation perhaps involving azine-like N-N bonds.For HC3N an equally rapid association has been observed by Buckley et al. with ICR (Ion Cyclotron Resonance) measurements at low pressures and this is suggestive of radiative association.The hydrogen atom transfer reaction of ionized cyanoacetylene with H2 is slow while similar reactions with CH4 and H2O are fast.The reaction with CO fails to transfer a proton.These results have implications for synthetic schemes for cyanoacetylene as proposed in recent models of the chemistry of interstellar gas clouds.Proton transfer was also observed to be curiously unfavourable with all other molecules having a proton affinity higher than (C3N)..Also, hydrogen-atom transfer was inefficient with the polar molecules HCN and HC3N.These results suggest that informations at close separations may lead to preferential alignment of the reacting ion and molecule which is not suited for proton transfer or hydrogen atom transfer.
- Fox, A.,Raksit, A. B.,Dheandhanoo, S.,Bohme, D. K.
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p. 399 - 403
(2007/10/02)
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