Abstract: The applicability of the Marcus rate-equilibrium formalism to the double-minimum potential energy surface for gas-phase SN2 reactions is proposed and used to develop a model for intrinsic nucleophilicity toward methyl centers. The key quantities in this model are the energy barriers to degenerate reactions of the form X-CH3X-XCH3. X-, in which the reacting species are ion-molecule cluster intermediates. Available experimental and ...
