Strong temperature dependence of water reorientation in hydrophobic hydration shells

We study the temperature dependence of the orientational mobility of water molecules solvating hydrophobic molecular groups with femtosecond midinfrared spectroscopy. We observe that these dynamics show a strong temperature dependence. At temperatures <30 degrees C the solvating water molecules show a reorientation time >10 ps, which is more than four times slower than in bulk water. With increasing temperature, the reorientation of the solvating molecules strongly accelerates and becomes much more equal to the reorientation rate of the molecules in the bulk liquid. These observations indicate that water molecules form relatively rigid solvation structures around hydrophobic molecular groups that melt at elevated temperatures.