Abstract
Translational energy dependence of reaction kinetics and internal energy depositions in reaction products were examined for gas-phase SN2 reactions of Cl- and F- with NCCO2CH3 and CF3CO2CH3 in a Fourier transform ion cyclotron resonance mass spectrometer (FTICR). The energy dependence of the kinetics was examined by measuring the SN2 rate constants as a function of reactant ion translational energies and by comparing the experimental results with those calculated using RRKM theory. Negative kinetic energy dependence was observed, and the changes of rate constants agree with RRKM theory predictions. The internal energy deposition in the SN2 products was examined by measuring the fraction of secondary fragments resulting from dissociation of the ionic SN2 product. A statistical model was used to calculate the statistical fraction of internally excited SN2 product ion under thermal conditions. For the least exothermic reaction (<20 kcal/mol), the measured fraction of secondary ion is comparable to the statis...
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