Density hysteresis of heavy water confined in a nanoporous silica matrix

Abstract

A neutron scattering technique was developed to measure the density of heavy water confined in a nanoporous silica matrix in a temperature-pressure range, from 300 to 130 K and from 1 to 2,900 bars, where bulk water will crystalize. We observed a prominent hysteresis phenomenon in the measured density profiles between warming and cooling scans above 1,000 bars. We interpret this hysteresis phenomenon as support (although not a proof) of the hypothetical existence of a first-order liquid-liquid phase transition of water that would exist in the macroscopic system if crystallization could be avoided in the relevant phase region. Moreover, the density data we obtained for the confined heavy water under these conditions are valuable to large communities in biology and earth and planetary sciences interested in phenomena in which nanometer-sized water layers are involved.confined water | equation of state | liquid-liquid critical phenomenon I n many biological and geological systems, water resides in pores of nanoscopic dimensions, or close to hydrophilic or hydrophobic surfaces, comprising a layer of water, one or two molecules thick, with properties often different from the bulk. Such "confined" or "interfacial" water has attracted considerable attention, due to its fundamental importance in many processes, such as protein folding, concrete curing, corrosion, molecular and ionic transport, etc. (1-3). However, our understanding of the numerous physicochemical anomalies of confined water, and indeed of bulk water, is still incomplete. Basic gaps persist, among which the most interesting one is the origin of the unusual behavior of water in the supercooled region where water remains in the liquid state below the melting point (4-7). Recent studies have aimed at explaining anomalies such as the density maximum and minimum (8-10), and the apparent divergence of the thermodynamic response functions at 228 K at ambient pressure (11). The three major hypothesized scenarios currently under scrutiny are the "singularity-free (SF) scenario" (12, 13), the "liquidliquid critical point (LLCP) scenario" (14, 15), and the "critical point-free (CPF) scenario" (16). It is hypothesized, by all these three scenarios, that in the low temperature range bulk water is composed of a mixture of two structurally distinct liquids: the low-density liquid (LDL) and the high-density liquid (HDL). They are respectively the thermodynamic continuation of the low-density amorphous ice (LDA) and high-density amorphous ice (HDA) into the liquid state. Evidence of a first-order phase transition between LDA and HDA has been reported since 1985 (17-20). Subsequently, several experimental findings have been interpreted as support of the hypothetical existence of two different structural motifs of liquid water (21-27). However, some of the interpretations have been questioned (28,29). So far, direct evidence of a first-order liquid-liquid phase transition between LDL and HDL, as a thermodynamic extension of the first-order transition established in the am...

Effects of confinement between attractive and repulsive walls on the thermodynamics of an anomalous fluid

“…Nevertheless, our conclusions do not exclude that the LLCP could be accessible also in strong hydrophilic confinement, such as in Ref.s [86,[92][93][94][95], because our study does not consider the effect of curvature of the confining walls on the crystallization rate. It is reasonable to hypothesize that the curvature would diminish the crystallization rate, making the critical region near the LLCP accessible also in strongly confined water.…”

Polymorphism and polyamorphism in bilayer water confined to slit nanopore under high pressure

“…For water confined to cylindrical pores (quasi-1D confinement), two recent experiments have demonstrated the existence of the low-density liquid (LDL) and prominent density hysteresis phenomenon, suggesting the possible existence of a first-order liquid-liquid phase transition in supercooled water (12,13). Evidence of amorphous-to-amorphous transition in quasi-1D pores, however, has not been observed either from experiments or simulations.…”

Finite-size scaling investigation of the liquid-liquid critical point in ST2 water and its stability with respect to crystallization

“…The hypothesis of the critical point also allows one to understand X-ray spectroscopy results, [16][17][18][19] explains the increasing correlation length in bulk water upon cooling as found experimentally, 20 the hysteresis effects, 21 and the dynamic behavior of protein hydration water. [22][23][24] It would be consistent with a range of thermodynamical and dynamical anomalies [25][26][27][28][29][30][31][32][33] and experiments.…”