Ultrafast vibrational dynamics at water interfaces.

Time-resolved sum-frequency vibrational spectroscopy permits the study of hitherto neglected ultrafast vibrational dynamics of neat water interfaces. Measurements on interfacial bonded OH stretch modes revealed relaxation behavior on sub-picosecond time scales in close resemblance to that of bulk water. Vibrational excitation is followed by spectral diffusion, vibrational relaxation, and thermalization in the hydrogen-bonding network. Dephasing of the excitation occurs in </=100 femtoseconds. Population relaxation of the dangling OH stretch was found to have a time constant of 1.3 picoseconds, the same as that for excitation transfer between hydrogen-bonded and unbonded OH stretches of water molecules surrounded by acetone.