Vibrational Förster transfer to hydrated protons

Abstract

We have studied the influence of excess protons on the vibrational energy relaxation of the O-H and O-D stretching modes in water using femtosecond pump-probe spectroscopy. Without excess protons, we observe exponential decays with time constants of 1.7 and 4.3 ps for the bulk and anion bound O-D stretch vibrations. The addition of protons introduces a new energy relaxation pathway, which leads to an increasingly nonexponential decay of the O-D stretch vibration. This new pathway is attributed to a distance-dependent long range dipole-dipole (Forster) interaction between the O-D stretching vibration and modes associated with dissolved protons. The high efficiency of hydrated protons as receptors of vibrational energy follows from the very large absorption cross section and broad bandwidth of protons in water. For a proton concentration of 1M we find that Forster energy transfer occurs over an average distance of 4.5 A, which corresponds to a separation of about two water molecules.