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dc.contributor.authorGonzales, AC-
dc.contributor.authorReid, ID-
dc.contributor.authorGarner, DM-
dc.contributor.authorSenba, M-
dc.contributor.authorFleming, DG-
dc.contributor.authorArseneau, DJ-
dc.contributor.authorKempton, JR-
dc.identifier.citationJournal of Chemical Physics , 91(10): 6164 - 6176, 1989en_US
dc.descriptionCopyright @ 1989 American Institute of Physicsen_US
dc.description.abstractBimolecular rate constants for the thermal chemical reactions of muonium (Mu) with the halogen gases—Mu+X2→MuX+X—are reported over the temperature ranges from 500 down to 100, 160, and 200 K for X2=F2,Cl2, and Br2, respectively. The Arrhenius plots for both the chlorine and fluorine reactions show positive activation energies Ea over the whole temperature ranges studied, but which decrease to near zero at low temperature, indicative of the dominant role played by quantum tunneling of the ultralight muonium atom. In the case of Mu+F2, the bimolecular rate constant k(T) is essentially independent of temperature below 150 K, likely the first observation of Wigner threshold tunneling in gas phase (H atom) kinetics. A similar trend is seen in the Mu+Cl2 reaction. The Br2 data exhibit an apparent negative activation energy [Ea=(−0.095±0.020) kcal mol−1], constant over the temperature range of ∼200–400 K, but which decreases at higher temperatures, indicative of a highly attractive potential energy surface. This result is consistent with the energy dependence in the reactive cross section found some years ago in the atomic beam data of Hepburn et al. [J. Chem. Phys. 69, 4311 (1978)]. In comparing the present Mu data with the corresponding H atom kinetic data, it is found that Mu invariably reacts considerably faster than H at all temperatures, but particularly so at low temperatures in the cases of F2 and Cl2. The current transition state calculations of Steckler, Garrett, and Truhlar [Hyperfine Interact. 32, 779 (986)] for Mu+X2 account reasonably well for the rate constants for F2 and Cl2 near room temperature, but their calculated value for Mu+Br2 is much too high. Moreover, these calculations seemingly fail to account for the trend in the Mu+F2 and Mu+Cl2 data toward pronounced quantum tunneling at low temperatures. It is noted that the Mu kinetics provide a crucial test of the accuracy of transition state treatments of tunneling on these early barrier HX2 potential energy surfaces.en_US
dc.description.sponsorshipNSERC (Canada), Donors of the Petroleum Research Fund, administered by the American Chemical Society, for their partial support of this research and the Canada Council.en_US
dc.publisherAmerican Institute of Physicsen_US
dc.subjectPotential energy surfacesen_US
dc.subjectChemical reaction kineticsen_US
dc.titleReaction kinetics of muonium with the halogen gases (F2, Cl2, and Br2)en_US
dc.typeResearch Paperen_US
pubs.organisational-data/Brunel/Brunel (Active)-
pubs.organisational-data/Brunel/Brunel (Active)/School of Engineering & Design-
pubs.organisational-data/Brunel/School of Engineering & Design-
Appears in Collections:Electronic and Computer Engineering
Dept of Electronic and Electrical Engineering Research Papers

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