Application of Marcus theory to gas-phase SN2 reactions: experimental support of the Marcus theory additivity postulate

Through the analysis of sufficiently fast identity exchange reactions, the Marcus theory additivity postulate has been tested and verified for two sets of gas-phase S N 2 reactions: X - +RCH 2 Y→XCH 2 R+Y - (where X and Y=Cl and/or Br and R=CN, C 6 H 5 ). Statistical RRKM theory, within the microcanonical variational transition state (μVTS) approximation, is used to interpret the experimental kinetic data for each reaction to intimate the activation energies relative to separated reactants. Complexation energie, determined experimentally, are used in conjunction with the data from the RRKM analysis to obtain potential surface energetics