Vibrational spectroscopy of HOD in liquid D2O.: VI.: Intramolecular and intermolecular vibrational energy flow

In a previous theoretical study [J. Chem. Phys. 117, 5827 (2002)] we calculated the vibrational lifetimes of the three fundamentals of HOD in liquid D2O. In that calculation the D2O solvent was treated as rigid, not allowing for the possibility of intermolecular vibrational energy transfer as a relaxation mechanism. In this paper we use both flexible and rigid solvent models, enabling us to include the possibility of intermolecular vibrational energy transfer, and also to estimate branching ratios for vibrational and nonvibrational relaxation channels. Our theoretical value for the lifetime of the OH stretch decreases modestly from 2.7 ps (in the original calculation) to 2.3 ps, which should be compared to the experimental value of about 1 ps. The lifetime of the OD stretch decreases dramatically from 18 ps to 390 fs due to resonant energy transfer to the solvent stretch. Our lifetime value for the bend actually increases from 220 to 380 fs, not because of the vibrational energy transfer channel, but rather because we find that Fermi's Golden Rule (used in the original calculation) breaks down for this very fast process. We have calculated all the state-to-state rate constants for the low-lying vibrational energy levels of HOD, which allows us to construct and solve the vibrational master equation. We find that after excitation of the OH stretch, population flows into the HOD bend states (and to a lesser extent the OD stretch of HOD) on the time scale of 1 ps, in agreement with recent infrared pump/Raman probe measurements of Dlott and co-workers. From our results we estimate that for each quantum of OH stretch excitation, 0.26 quanta of solvent stretch is excited by direct intermolecular energy transfer, and yet we find, surprisingly, that there is almost no direct excitation of solvent bend. On the other hand, we suggest that because of the intramolecular Fermi resonance in D2O, rapid intramolecular vibrational relaxation occurs from solvent stretch to solvent bend. This would account for the experimental observation of solvent stretch and bend excitations on the time scale of 1 ps after the OH stretch is excited. (C) 2003 American Institute of Physics.