Vibrational spectroscopy of HOD in liquid D2O.: I.: Vibrational energy relaxation

We present calculations of the vibrational lifetimes for the three fundamentals of HOD in liquid D2O. The calculations build on the work of Oxtoby and of Rey and Hynes, but also introduce some new ideas, the most important of which is a self-consistent renormalization scheme for determining the system and bath Hamiltonians for a given vibrational state of the HOD molecule. Our result for T-1 for the OH stretch fundamental is 2.7 ps, which is about a factor of 3 larger than the experimental number. We suggest that including solvent vibrations may bring theory in closer agreement with experiment. (C) 2002 American Institute of Physics.