Elementary Steps in Excited-State Proton Transfer

Abstract

The absorption of a photon by a hydroxy-aromatic photoacid triggers a cascade of events contributing to the overall phenomenon of intermolecular excited-state proton transfer. The fundamental steps involved were studied over the last 20 years using a combination of theoretical and experimental techniques. They are surveyed in this sequel in sequential order, from fast to slow. The excitation triggers an intramolecular charge transfer to the ring system, which is more prominent for the anionic base than the acid. The charge redistribution, in turn, triggers changes in hydrogen-bond strengths that set the stage for the proton-transfer step itself. This step is strongly influenced by the solvent, resulting in unusual dependence of the dissociation rate coefficient on water content, temperature, and isotopic substitution. The photolyzed proton can diffuse in the aqueous solution in a mechanism that involves collective changes in hydrogen-bonding. On longer times, it may recombine adiabatically with the excited base or quench it. The theory for these diffusion-influenced geminate reactions has been developed, showing nice agreement with experiment. Finally, the effect of inert salts, bases, and acids on these reactions is analyzed.