Large-scale structure and hyperuniformity of amorphous ices

We investigate the large-scale structure of amorphous ices and transitions between their different forms by quantifying their large-scale density fluctuations. Specifically, we simulate the isothermal compression of low-density amorphous ice (LDA) and hexagonal ice (Ih) to produce high-density amorphous ice (HDA). Remarkably, both HDA and LDA are nearly hyperuniform, meaning that they are characterized by an anomalous suppression of large-scale density fluctuations. By contrast, in correspondence with both non-equilibrium phase transitions to HDA, the presence of structural heterogeneities strongly suppresses the hyperuniformity and, remarkably, the system becomes hyposurficial (devoid of "surface-area" fluctuations). Our investigation challenges the largely accepted "frozen-liquid" picture, which views glasses as structurally arrested liquids. Beyond implications for water, our findings enrich our understanding of the structural transformations that occur in glasses with varying pressures

Structural Order for One-Scale and Two-Scale Potentials

We perform molecular dynamics simulations to investigate the relationship between structural order and water-like dynamic and thermodynamic anomalies in spherically-symmetric potentials having either one or two characteristic length scales. %The first potential has only one length scale which is the diameter of the ramp %without the hard core, and the second potential has two length scales: one is the %diameter of a ramp(softcore) and another one is the diameter of a %hard core with a ratio of 1.76. Structural order is characterized by translational and orientational order parameters. %analogous to those used in previous cases for water and %silica.Only the two-scale ramp potential exhibits properties %remarkably similar to those found for water and silica regarding the %relationship between structural order, dynamic anomalies, and thermodynamic %anomalies. We find that (i) dynamic and thermodynamic anomalies exist for both one-scale and two-scale ramp potentials, and (ii) water-like structural order anomalies exist only for the two-scale ramp potential. Our findings suggest that the water-like relationship between structural order and anomalies is related to the presence of two different length scales in the potential.Comment: 12 pages, 5 figure

Phase Diagram of Water Confined by Graphene

The behavior of water confined at the nanoscale plays a fundamental role in biological processes and technological applications, including protein folding, translocation of water across membranes, and filtration and desalination. Remarkably, nanoscale confinement drastically alters the properties of water. Using molecular dynamics simulations, we determine the phase diagram of water confined by graphene sheets in slab geometry, at T = 300 K and for a wide range of pressures. We find that, depending on the confining dimension D and density σ, water can exist in liquid and vapor phases, or crystallize into monolayer and bilayer square ices, as observed in experiments. Interestingly, depending on D and σ, the crystal-liquid transformation can be a first-order phase transition, or smooth, reminiscent of a supercritical liquid-gas transformation. We also focus on the limit of stability of the liquid relative to the vapor and obtain the cavitation pressure perpendicular to the graphene sheets. Perpendicular cavitation pressure varies non-monotonically with increasing D and exhibits a maximum at D ≈ 0.90 nm (equivalent to three water layers). The effect of nanoconfinement on the cavitation pressure can have an impact on water transport in technological and biological systems. Our study emphasizes the rich and apparently unpredictable behavior of nanoconfined water, which is complex even for graphene

Relation between the High Density Phase and the Very-High Density Phase of Amorphous Solid Water

It has been suggested that high-density amorphous (HDA) ice is a structurally arrested form of high-density liquid (HDL) water, while low-density amorphous (LDA) ice is a structurally arrested form of low-density liquid (LDL) water. Recent experiments and simulations have been interpreted to support the possibility of a second "distinct" high-density structural state, named very high-density amorphous (VHDA) ice, questioning the LDL-HDL hypothesis. We test this interpretation using extensive computer simulations, and find that VHDA is a more stable form of HDA and that in fact VHDA should be considered as the amorphous ice of the quenched HDL.Comment: 5 pages, 4 fig

Structure of the First and Second Neighbor Shells of Water: Quantitative Relation with Translational and Orientational Order

We perform molecular dynamics simulation of water using the TIP5P model to quantify structural order in both the first shell (defined by four nearest neighbors)and second shell (defined by twelve next-nearest neighbors) of a central water molecule. We find the anomalous decrease of orientational order upon compression occurs in both shells, but the anomalous decrease of translational order upon compression occurs {\it mainly in the second shell}. The decreases of translational and orientational orders upon compression ("structural anomaly") are thus correlated only in the second shell. Our findings quantitatively confirm the qualitative idea that the thermodynamic, dynamic and structural anomalies of water are related to changes in the second shell upon compression.Comment: 12 pages, 5 figure

A Family of Tunable Spherically-Symmetric Potentials that Span the Range from Hard Spheres to Water-like Behavior

We investigate the equation of state, diffusion coefficient, and structural order of a family of spherically-symmetric potentials consisting of a hard core and a linear repulsive ramp. This generic potential has two characteristic length scales: the hard and soft core diameters. The family of potentials is generated by varying their ratio, $\lambda$. We find negative thermal expansion (thermodynamic anomaly) and an increase of the diffusion coefficient upon isothermal compression (dynamic anomaly) for $0\leq\lambda<6/7$. As in water, the regions where these anomalies occur are nested domes in the ($T, \rho$) or ($T, P$) planes, with the thermodynamic anomaly dome contained entirely within the dynamic anomaly dome. We calculate translational and orientational order parameters ($t$ and $Q_6$), and project equilibrium state points onto the ($t, Q_6$) plane, or order map. The order map evolves from water-like behavior to hard-sphere-like behavior upon varying $\lambda$ between 4/7 and 6/7. Thus, we traverse the range of liquid behavior encompassed by hard spheres ($\lambda=1$) and water-like ($\lambda\sim4/7$) with a family of tunable spherically-symmetric potentials by simply varying the ratio of hard to soft-core diameters. Although dynamic and thermodynamic anomalies occur almost across the entire range $0\leq\lambda\leq1$, water-like structural anomalies (i.e., decrease in both $t$ and $Q_6$ upon compression and strictly correlated $t$ and $Q_6$ in the anomalous region) occur only around $\lambda=4/7$. Water-like anomalies in structure, dynamics and thermodynamics arise solely due to the existence of two length scales, orientation-dependent interactions being absent by design.Comment: total 21 pages, 6 figure

Liquid-Liquid Phase Transition and Glass Transition in a Monoatomic Model System

We review our recent study on the polyamorphism of the liquid and glass states in a monatomic system, a two-scale spherical-symmetric Jagla model with both attractive and repulsive interactions. This potential with a parametrization for which crystallization can be avoided and both the glass transition and the liquid-liquid phase transition are clearly separated, displays water-like anomalies as well as polyamorphism in both liquid and glassy states, providing a unique opportunity to study the interplay between the liquid-liquid phase transition and the glass transition. Our study on a simple model may be useful in understanding recent studies of polyamorphism in metallic glasses