Double Proton Transfer Reactions with Plateau-Like Transition State Regions:  Pyrazole−Trifluoroacetic Acid Clusters

The double proton transfer reactions between carboxylic acids and pyrazole were studied by computational methods up to the coupled-cluster level. Introduction of substituents allowed for a systematic modulation of the reaction profile, resulting in imaginary frequencies of the associated transition states between −1180 and −45 cm^-1. In the latter case, a local transition state is replaced by an extremely flat (plateaulike) transition region, which constitutes the transition from a concerted toward a stepwise mechanism. Vertical excitation energies along the reaction path reveal that the feature of a plateau in the ground state is mirrored in the excited states.