By confining water in nanopores of silica glass, we can bypass the crystallization and study the pressure effect on the dynamical behavior in deeply supercooled state using neutron scattering. We observe a clear evidence of a cusplike fragile-to-strong (FS) dynamic transition. Here we show that the transition temperature decreases steadily with an increasing pressure, until it intersects the homogenous nucleation temperature line of bulk water at a pressure of 1600 bar. Above this pressure, it is no longer possible to discern the characteristic feature of the FS transition. Identification of this end point with the possible second critical point is discussed.

At low temperatures, proteins exist in a glassy state, a state that has no conformational flexibility and shows no biological functions. In a hydrated protein, at temperatures ≳220 K, this flexibility is restored, and the protein is able to sample more conformational substates, thus becoming biologically functional. This “dynamical” transition of protein is believed to be triggered by its strong coupling with the hydration water, which also shows a similar dynamic transition. Here we demonstrate experimentally that this sudden switch in dynamic behavior of the hydration water on lysozyme occurs precisely at 220 K and can be described as a fragile-to-strong dynamic crossover. At the fragile-to-strong dynamic crossover, the structure of hydration water makes a transition from predominantly high-density (more fluid state) to low-density (less fluid state) forms derived from the existence of the second critical point at an elevated pressure.

By confining water in nanopores, so narrow that the liquid cannot freeze, it is possible to explore its properties well below its homogeneous nucleation temperature T _H ≈ 235 K. In particular, the dynamical parameters of water can be measured down to 180 K, approaching the suggested glass transition temperature T _g ≈ 165 K. Here we present experimental evidence, obtained from Nuclear Magnetic Resonance and Quasi-Elastic Neutron Scattering spectroscopies, of a well defined decoupling of transport properties (the self-diffusion coefficient and the average translational relaxation time), which implies the breakdown of the Stokes–Einstein relation. We further show that such a non-monotonic decoupling reflects the characteristics of the recently observed dynamic crossover, at ≈225 K, between the two dynamical behaviors known as fragile and strong, which is a consequence of a change in the hydrogen bond structure of liquid water.

By confining water in a nanoporous structure so narrow that the liquid could not freeze, it is possible to study properties of this previously undescribed system well below its homogeneous nucleation temperature T _H = 231 K. Using this trick, we were able to study, by means of a Fourier transform infrared spectroscopy, vibrational spectra (HOH bending and OH-stretching modes) of deeply supercooled water in the temperature range 183 < T < 273 K. We observed, upon decreasing temperature, the building up of a new population of hydrogen-bonded oscillators centered around 3,120 cm ⁻¹ , the contribution of which progressively dominates the spectra as one enters into the deeply supercooled regime. We determined that the fractional weight of this spectral component reaches 50% just at the temperature, T _L ≈ 225 K, where the confined water shows a fragile-to-strong dynamic cross-over phenomenon [Ito, K., Moynihan, C. T., Angell, C. A. (1999) Nature 398:492–494]. Furthermore, the fact that the corresponding OH stretching spectral peak position of the low-density-amorphous solid water occurs exactly at 3,120 cm ⁻¹ [Sivakumar, T. C., Rice, S. A., Sceats, M. G. (1978) J. Chem. Phys. 69:3468–3476.] strongly suggests that these oscillators originate from existence of the low-density-liquid phase derived from the occurrence of the first-order liquid–liquid (LL) phase transition and the associated LL critical point in supercooled water proposed earlier by a computer molecular dynamics simulation [Poole, P. H., Sciortino, F., Essmann, U., Stanley, H. E. (1992) Nature 360:324–328].

By means of a nuclear magnetic resonance experiment, we give evidence of the existence of a fragile-to-strong dynamic crossover transition (FST) in confined water at a temperature TL=223±2K. We have studied the dynamics of water contained in 1D cylindrical nanoporous matrices (MCM-41-S) in the temperature range 190–280K, where experiments on bulk water were so far hampered by crystallization. The FST is clearly inferred from the T dependence of the inverse of the self-diffusion coefficient of water (1∕D) as a crossover point from a non-Arrhenius to an Arrhenius behavior. The combination of the measured self-diffusion coefficient D and the average translational relaxation time ⟨τT⟩, as measured by neutron scattering, shows the predicted breakdown of Stokes-Einstein relation in deeply supercooled water.

Small angle neutron scattering (SANS) is used to measure the density of heavy water contained in 1D cylindrical pores of mesoporous silica material MCM-41-S-15, with pores of diameter of 15 ± 1 Å. In these pores the homogenous nucleation process of bulk water at 235 K does not occur, and the liquid can be supercooled down to at least 160 K. The analysis of SANS data allows us to determine the absolute value of the density of D ₂ O as a function of temperature. We observe a density minimum at 210 ± 5 K with a value of 1.041 ± 0.003 g/cm ³ . We show that the results are consistent with the predictions of molecular dynamics simulations of supercooled bulk water. Here we present an experimental report of the existence of the density minimum in supercooled water, which has not been described previously.