We study the hydrogen-bond and reorientation dynamics of weakly hydrogen-bonded water molecules by studying their spectral diffusion and anisotropy dynamics with polarization-resolved two-color femtosecond mid-infrared spectroscopy. We selectively excite weakly hydrogen-bonded water molecules by tuning a relatively narrow band excitation pulse far into the high-frequency wing of the O–D stretch vibration of HDO molecules in H2O water. We observe that the spectral diffusion and the anisotropy both show pronounced biexponential dynamics. On the basis of previous work, the fast component of the spectral dynamics with a time constant of 100 fs is assigned to rapid hydrogen-bond switching events. We observed that these switching events lead to a pronounced effect on the anisotropy of the excited O–D groups, which shows that the spectral relaxation is accompanied by a large change of the orientation of the O–D groups. The slow component of the spectral relaxation can be assigned to the collective structural reorganization of the hydrogen-bond network of liquid water. With increasing temperature, the spectral relaxation shows a similar acceleration as the average molecular reorientation, showing that these processes are intimately connected.

J. Phys. Chem. B
Ultrafast Spectroscopy

van der Post, S.T, & Bakker, H.J. (2014). Femtosecond Mid-infrared Study of the Reorientation of Weakly Hydrogen-bonded Water Molecules. J. Phys. Chem. B, 118(28), 8179–8189. doi:10.1021/jp501240e