Water jump reorientation: from theoretical prediction to experimental observation

Liquid water is remarkably labile in reorganizing its hydrogen-bond (HB) network through the breaking and forming of HBs. This rapid restructuring, which occurs on the picosecond time scale, is critical not only for many of the pure liquid's special features but also for a range of aqueous media phenomena, including chemical reactions and protein activity. An essential part of the HB network reorganization is water molecule reorientation, which has long been described as Debye rotational diffusion characterized by very small angular displacements. Recent theoretical work, however, has presented a starkly contrasting picture: a sudden, large-amplitude jump mechanism, in which the reorienting water molecule rapidly exchanges HB partners in what amounts to an activated chemical reaction. In this Account, we first briefly review the jump mechanism and then discuss how it is supported by a series of experiments. These studies range from indirect indications to direct characterization of the jumps through pioneering two-dimensional infrared spectroscopy (2D-IR), the power of which accords it a special focus here. The scenarios in which experimental signatures of the jump mechanism are sought increase in complexity throughout the Account, beginning with pure water. Here 2D-IR in combination with theory can give a glimpse of the jumps, but the tell-tale markers are not pronounced. A more fruitful arena is provided by aqueous ionic solutions. The difference between water-water and water-anion HB strengths provides the experimental handle of differing OH stretch frequencies; in favorable cases, the kinetic exchange of a water between these two sites can be monitored. Sole observation of this exchange, however, is insufficient to establish the jump mechanism. Fortunately, 2D-IR with polarized pulses has demonstrated that HB exchange is accompanied by significant angular displacement, with an estimated jump angle similar to theoretical estimates. The Janus-like character of amphiphilic solutes, with their hydrophobic and hydrophilic faces, presents a special challenge for theory and experiment. Here a consensus on the 2D-IR interpretation has not yet been achieved; this lack of accord impedes the understanding of, for example, biochemical solutes and interfaces. We argue that the influence of hydrophobic groups on water jumps is only modest and well accounted for by an excluded volume effect in the HB exchange process. Conversely, hydrophilic groups have an important influence when their HB strength with water differs significantly from that of the water-water HB. The power of 2D-IR is argued to be accompanied by subtleties that can lead to just the opposite and, in our view, erroneous conclusion. We close with a prediction that a hydrophobic surface offers an arena in which the dynamics of "dangling" water OHs, bereft of a HB, could provide a 2D-IR confirmation of water jumps.