Vibrational relaxation of the bending mode of HDO in liquid D2O

The vibrational relaxation of the bending mode of HDO in liquid D₂O has been studied using time-resolved mid-infrared pump-probe spectroscopy. At short delays, the transient spectrum clearly shows the v = 1 --> 2 induced absorption and v = 1 --> 0 bleaching and stimulated emission, whereas at long delays, the transient spectrum is dominated by the spectral changes caused by the temperature increase in the sample after vibrational relaxation. From the decay of the v = 1 --> 2 induced absorption, we obtain an estimate of 390 ± 50 fs for the vibrational lifetime, in surprisingly good agreement with recent theoretical predictions. In the v = 0 --> 1 frequency region, the decay of the absorption change involves a second, slower component, which suggests that after vibrational relaxation the system is not yet in thermal equilibrium.