Energy Requirements for a Chemical Reaction. 2. Electron Transfer to SbF5 and SnCl4

Article abstract of DOI:10.1021/ja00212a018

We have measured the integral reactive cross section for the electron-transfer reaction A + D -> A^- + D⁺, where the electron acceptor A is SnCl4 or SbF5 and the electron donor D is one of three amines.By using seeded nozzle beams we are abble to vary separately the translational and vibrational energies.The cross sections rise rapidly above a threshold which is equal to or just above the thermodynamic, adiabatic threshold for the reaction.Vibrational energy in this region plays little or no role in the reaction.At higher energies the dependence on translational energy levels off and then drops rapidly.In this region an increase in vibrational energy makes a large increase in the cross section.At high energies, some of the product ions dissociate.The ratios of the intensities of the various products depends largely on translational energy even though the overall cross section depends markedly on vibrational energy.