Vibrational spectroscopy of HOD in liquid D_2O. I. Vibrational energy relaxation

摘要

We present calculations of the vibrational lifetimes for the three fundamentals of HOD in liquid D_2O. 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 Mamiltonians 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 3larger than the experimental number. We suggest that including solvent vibrations may bring theory in closer agreement with experiment.