Abstract
Proton or hydrogen transfers, basic chemical reactions, proceed either by thermally activated barrier crossing or via tunneling. Studies of molecules undergoing single or double proton or hydrogen transfer in the ground or excited electronic state reveal that tunneling can dominate under conditions usually considered to favor the thermal process. Moreover, the tunneling probability strongly varies for excitation of certain vibrational modes, which changes the effective barrier and/or proton transfer distance. When the reaction is fast compared to vibrational relaxation, the mode selectivity can still be maintained for molecules in solutions at 293 K. These observations point to dangers of relating the calculated minimum energy paths and the associated barriers to the experimentally obtained activation energies. The multidimensional character of the reaction coordinate is obvious; it can dramatically change for slowly and rapidly relaxing environments. We postulate that the hydrogen bond definition should be extended by specifically including the role of molecular vibrations.