- Infrared diode laser and microwave spectra and molecular structure of an unstable molecule, FBO
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The FBO molecule was generated by a dc discharge in a mixture of BF3, O2, and He and its vibration-rotation and rotation spectra were observed by using infrared diode laser spectroscopy and microwave spectroscopy, respectively.The ν1 B-O stretching mode of F11BO and F10BO and the ν1 +ν2 - ν2 hot band of F11BO were observed in the region 2050 to 2140 cm-1.Subsequently, the pure rotational spectrum was observed for the following isotopic species: F11BO, F10BO, F11B18O, and F10B18O.The rotational, centrifugal distortion, and 1-type doubling constants were determined from the observed spectra, and the partial rs structure of FBO was calculated from rs coordinates and the first moment equation to be r(F-B) = 1.2833(7) Angstroem and r(B-O) = 12072(7) Angstroem.
- Kawashima, Yoshiyuki,Kawaguchi, Kentarou,Endo, Yasuki,Hirota, Eizi
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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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- Kinetics of Some Gas-Phase Elementary Reactions of Boron Monofluoride
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Rate coefficients for some elementary bimolecular reactons involving the molecule BF have been measured in a gas-phase flow tube facility.The BF + Cl2 reaction was studied from 295 to 881 K; the rate coefficient is temperature-independent with value of (1.4 +/- 0.2) X 10-11 cm3/(molecule s).Reaction of BF with O2 was studied between 675 and 1033 K; the inferred Arrhenius rate is 1.8 X 10-11 exp(-7240/Τ) cm3/(molecule s).Room temperature rate coefficients for BF + O and BF + NO2 were determined to be (1.8 +/- 0.4) X 10-10 and (2.1 +/- 0.3) X 10-13 cm3/(molecule s), respectively.Uncertainties quoted are 95percent confidence limits derived from random errors in individual measurements.Reaction of BF was undetectable upon mixing with H2O, HF, CO2, NO, N2O, SO2, or CH3Cl.Upper limits are given for rate coefficients for these reactions.Boron monofluoride proved to be less reactive than other simple boron species which have been studied recently, viz, boron atoms and boron monoxide.Results for BF are compared with available rate information for reactions of isoelectronic CO and N2.
- Light, G. C.,Herm, R. R.,Matsumoto, J. H.
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p. 5066 - 5074
(2007/10/02)
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