OD stretch vibrational relaxation of HOD in liquid to supercritical H(2)O

The population relaxation of the OD stretching vibration of HOD diluted in H(2)O is studied by time-resolved infrared pump-probe spectroscopy for temperatures between 278 and 663 K in the density range 0.281 OD stretching transition at low temperatures show a delay between excited state decay and formation of the thermalized spectrum pointing to an intermediately populated state. Above 400 K, the rates of excited state decay and ground state recovery become equivalent and the intermediate state is not detectable anymore. Over the entire thermodynamic range, the derived OD stretch relaxation rate constant k(r) depends linearly on the static dielectric constant epsilon of water, indicating a correlation of k(r) with the average hydrogen bond connectivity of HOD within the H(2)O network. However, in contrast to the OH stretch relaxation rate constant of the complementary system of HOD in D(2)O, the low density data of k(r)(epsilon) extrapolate to a nonzero intercept for epsilon-->1. Our analysis suggests that at ambient conditions the OD excited state is mainly depopulated by a direct v=1-->0 transition, avoiding the excited v=1 HOD bending state. Therefore, at room temperature the detected intermediate is assigned to a nonthermalized state with respect to nuclear degrees of freedom of the solvent molecules, and subsequent formation of the final product spectrum is related to a rearrangement of the hydrogen bond network. Passing over to the gas phase the excited OD stretch state shifts into close resonance with the HOD bend overtone, thereby opening up an additional relaxation channel.