Gibbs energies of activation for reacting systems with multiple reactant‐state and transition‐state conformations

Three distinct procedures for obtaining the effective Gibbs energies of activation from computed a reaction involving multiple reactant-state (RS) and transition-state (TS) conformers are shown to be equivalent. If Boltzmann-weighted average RS TS evaluated, then energy contribution entropy mixing both must also included in order obtain correct value activation. Application solvolytic 4,4′-dimethoxybenzhydrylpyridinium cation, which is satisfy Curtin-Hammett principle with rapid interconversion conformers, demonstrates use each procedure evaluation