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

Article abstract of DOI:10.1063/1.451687

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 SF6^-*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.

Full text of DOI:10.1063/1.451687

Role of binding energies in A−B and AB− complexes in the kinetics of gas
phase electron transfer reactions: A−+B=A+B− involving perfluoro
compounds: SF6, C6F11CF3, C6F6
Swapan Chowdhury and Paul Kebarle
Citation: J. Chem. Phys. 85, 4989 (1986); doi: 10.1063/1.451687
View online: http://dx.doi.org/10.1063/1.451687
View Table of Contents: http://jcp.aip.org/resource/1/JCPSA6/v85/i9
Published by the American Institute of Physics.
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