Exothermic gas phase electron transfer reactions: A−+B=A+B−, where A and B are polyatomic molecules with positive electron affinities, generally proceed at collision rates. However, reactions involving A=SF6 or perfluorocycloalkanes have rates which decrease with the exothermicity of the reaction, becoming very slow at low exothermicity. Earlier work attributed this behavior to the presence of an energy barrier, due to a large geometry change for A− to A. The reaction coordinate used also involves the bond energies A− ⋅ B and A ⋅ B−. These were measured in the present work. It was found that the bond energy in SF−6 ⋅ B is much larger than in SF6 ⋅ B− . This difference increases the energy barrier very significantly and is thus an additional cause for the slow electron transfer. The bond energies for several other complexes like: Cl− ⋅ B, Cl− ⋅ SF6, Cl− ⋅ perfluorocyloalkanes, and Cl− ⋅ C6F6 were measured. These provide insights into the nature of the bonding involved. The work was performed with a pulsed electron high pressure mass spectrometer.
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1 November 1986
Research Article|
November 01 1986
Role of binding energies in A− ⋅ B and A ⋅ B− complexes in the kinetics of gas phase electron transfer reactions: A−+B=A+B− involving perfluoro compounds: SF6, C6F11CF3, C6F6
Swapan Chowdhury;
Swapan Chowdhury
Chemistry Department, University of Alberta, Edmonton, Alberta T6G 2G2, Canada
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Paul Kebarle
Paul Kebarle
Chemistry Department, University of Alberta, Edmonton, Alberta T6G 2G2, Canada
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J. Chem. Phys. 85, 4989–4994 (1986)
Article history
Received:
May 12 1986
Accepted:
July 29 1986
Citation
Swapan Chowdhury, Paul Kebarle; Role of binding energies in A− ⋅ B and A ⋅ B− complexes in the kinetics of gas phase electron transfer reactions: A−+B=A+B− involving perfluoro compounds: SF6, C6F11CF3, C6F6. J. Chem. Phys. 1 November 1986; 85 (9): 4989–4994. https://doi.org/10.1063/1.451687
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