For decades, the enigma of the hydrophobic force has captured the imagination of scientists. In particular, Frank and Evans idea that the hydrophobic effect was mainly due to some kind of "iceberg" formation around a hydrophobic solute stimulated many experiments and molecular dynamics simulation studies. A better understanding of hydrophobic interactions will aid understanding in many contexts including protein structural dynamics and functioning in biological systems. In this Account, we present results of two-dimensional infrared (2D IR) spectroscopy experiments on the OH-stretch vibrational mode of water molecules near hydrophobic groups in concentrated solutions with tetramethylurea (TMU). The frequency of the OH vibration is a sensitive probe for environmental dynamics and, in particular, for the strength of the hydrogen bond. Two-dimensional IR spectroscopy can trace time correlations of the vibrational frequency at the scale of hundreds of femtoseconds and thus provides valuable insight into the effect of hydrophobic solutes on the dynamics of a hydrogen-bond network. We compare the 2D spectroscopic results with molecular dynamics (MD) simulations to obtain a microscopic picture of hydrophobic solvation. We observe two different types of hydrogen-bond dynamics in the water/TMU mixtures. We attribute the "fast" (∼100 fs) dynamics to highly coordinated water molecular-jump reorientations and assigned the "slow (>1 ps) dynamics to water translational motions that are strongly suppressed by the TMU molecules. Molecular dynamics simulations demonstrate a clear correlation between the slowed dynamics and the translational mobility of water. This finding indicates that the molecular-jump reorientations are switched off near hydrophobic groups. The fifth water molecule, which is required to form a defect state in the tetrahedral surroundings, cannot approach the hydrogen-bonded pair to initiate the molecular jump. As a result, the rate of the jumping events sharply decreases, which, in turn, strongly slows the rotation of the water molecules. Our findings suggest that water molecules in the hydrophobic solvation shell do not exhibit an increased tetrahedral ordering compared with the bulk but that the hydrogen-bond dynamics in the two cases are different. This result also indicates that consideration of a hydrogen bond’s dynamics could be critical for its definition.

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Journal Acc. Chem. Res.
Bakulin, A.A, Liang, C, Jansen, T.L.C, Wiersma, D.A, Bakker, H.J, & Pshenichnikov, M.S. (2009). Hydrophobic solvation : a 2D IR spectroscopic inquest. Acc. Chem. Res., 42(9), 1229–1238. doi:10.1021/ar9000247