Hydrogen Bonding and Vibrational Energy Relaxation in Water−Acetonitrile Mixtures

Abstract

We present a study of the effect of hydrogen bonding on vibrational energy relaxation of the OH-stretching mode in pure water and in water−acetonitrile mixtures. The extent of hydrogen bonding is controlled by dissolving water at various concentrations in acetonitrile. Infrared frequency-resolved pump−probe measurements were used to determine the relative abundance of hydrogen-bonded versus non-hydrogen-bonded OH bonds in water−acetonitrile mixtures. Our data show that the main pathway for vibrational relaxation of the OH-stretching mode in pure water involves the overtone of the bending mode. Hydrogen bonding is found to accelerate the population relaxation from 3 ps in dilute solutions to 700 fs in neat water, as a result of increasing overlap between donor and acceptor modes. Hydroxyl groups that initially are not hydrogen bonded have two relaxation pathways: by direct nonresonant relaxation to the bending mode with a time constant of 12 ps or by making a hydrogen bond to a neighboring water molecule first (∼2 ps) and then relaxing as a hydrogen-bonded OH oscillator.