Journal of Physical Chemistry A, Vol.110, No.29, 9039-9050, 2006
Temperature dependence of excited-state proton transfer in water electrolyte solutions and water-methanol solutions
The reversible proton dissociation and geminate recombination of a photoacid is studied as a function of temperature in water electrolyte solutions and binary water-methanol mixtures, containing 0.1 and 0.2 mole fractions of methanol. 8-Hydroxypyrene-1,3,6-trisulfonate trisodium salt ( HPTS) is used as the photoacid. The experimental data are analyzed by the reversible geminate recombination model. We found that the slope of the logarithm of the proton-transfer rate constant as a function of the inverse of temperature (Arrhenius plot) in the liquid phase of these samples are temperature-dependent, while in the solid phase, the slope is nearly constant. The slope of the Arrhenius plot in frozen electrolyte solution is larger than that of the water-methanol mixtures, which is about the same as in pure water. Careful examination of the time-resolved emission in ice samples shows that the fit quality using the geminate recombination model is rather poor at relatively short times. We were able to get a better fit using an inhomogeneous kinetics model assuming the proton-transfer rate consists of a distribution of rates. The model is consistent with an inhomogeneous frozen water distribution next to the photoacid.