Vibrational Excitation Induced Proton Transfer in Hydrated Nafion Membranes

We study the energy relaxation and structural relaxation dynamics of hydrated protons in Nafion membranes at different hydration levels using femtosecond infrared transient absorption spectroscopy. At low hydration levels we observe that the excitation of the proton vibration of an Eigen-like proton hydration structure leads to a structural relaxation process in which the Eigen-like structure evolves to a Zundel-like proton hydration structure. This reorganization leads to a transfer of the proton charge and closely follows the mechanism of infrared-induced adiabatic proton transfer that has been proposed by S. Hammes-Schiffer, J. T. Hynes, and others. At high hydration levels, the spectral dynamics are dominated by vibrational energy relaxation and subsequent cooling of the proton hydration structures and the surrounding water molecules. Using a kinetic analysis of the transient spectral data, we determine the rates of proton transfer, vibrational energy relaxation, and cooling as a function of hydration level. We find that infrared-induced proton transfer occurs at all hydration levels but becomes less observable at high hydration levels due to the increasingly dominant influence of the vibrational energy relaxation.