Temperature dependence of excited-state proton transfer and geminate recombination processes in water and in glycerol-doped ice

The reversible proton dissociation and geminate recombination of photoacids was studied as a function of temperature in neat water, binary water mixture containing 0.6 mol% glycerol, and doped ice containing 0.6 mol% glycerol. The deuterium isotope effect on both condensed phases was also studied. 8-hydroxypyrene-1,3,6 trisulfonate trisodium salt was used as the electronically-excited-state proton emitter. The experimental data are analyzed by the Debye-Smoluchowski equation solved numerically with boundary conditions to account for the reversibility of the reaction. We propose a qualitative model to describe the unusual temperature dependence of the proton transfer rate in the liquid phase. We also propose a model for proton transfer in solid ice based on L-defects transport as proton acceptors. While in the liquid phase at t > 10 °C the proton dissociation rate constant is almost temperature independent, in glycerol-doped ice we find a large temperature dependence.