Identification of local structures in water from supercooled to ambient conditions.

Studies of water thermodynamics have long been tied to the identification of two distinct families of local structures, whose competition could explain the origin of the many thermodynamic anomalies and the hypothesized liquid-liquid critical point in water. Despite the many successes and insights gained, the structural indicators proposed throughout the years were not able to unequivocally identify these two families over a wide range of conditions. We show that a recently introduced indicator, Ψ, which exploits information on the hydrogen bond network connectivity, can reliably identify these two distinct local environments over a wide range of thermodynamic conditions (188-300 K and 0-13 kbar) and that close to the liquid-liquid critical point, the spatial correlations of density fluctuations are identical to those of the Ψ indicator. Our results strongly support the idea that water thermodynamic properties arise from the competition between two distinct and identifiable local environments.

A statistical mechanical model of supercooled water based on minimal clusters of correlated molecules.

In this paper, we apply a theoretical model for fluid state thermodynamics to investigate simulated water in supercooled conditions. This model, which we recently proposed and applied to sub- and super-critical fluid water [Zanetti-Polzi et al., J. Chem. Phys. 156(4), 44506 (2022)], is based on a combination of the moment-generating functions of the enthalpy and volume fluctuations as provided by two gamma distributions and provides the free energy of the system as well as other relevant thermodynamic quantities. The application we make here provides a thermodynamic description of supercooled water fully consistent with that expected by crossing the liquid-liquid Widom line, indicating the presence of two distinct liquid states. In particular, the present model accurately reproduces the Widom line temperatures estimated with other two-state models and well describes the heat capacity anomalies. Differently from previous models, according to our description, a cluster of molecules that extends beyond the first hydration shell is necessary to discriminate between the statistical fluctuation regimes typical of the two liquid states.

Encounter rates prime interactions between microorganisms.

Properties of microbial communities emerge from the interactions between microorganisms and between microorganisms and their environment. At the scale of the organisms, microbial interactions are multi-step processes that are initiated by cell-cell or cell-resource encounters. Quantification and rational design of microbial interactions thus require quantification of encounter rates. Encounter rates can often be quantified through encounter kernels-mathematical formulae that capture the dependence of encounter rates on cell phenotypes, such as cell size, shape, density or motility, and environmental conditions, such as turbulence intensity or viscosity. While encounter kernels have been studied for over a century, they are often not sufficiently considered in descriptions of microbial populations. Furthermore, formulae for kernels are known only in a small number of canonical encounter scenarios. Yet, encounter kernels can guide experimental efforts to control microbial interactions by elucidating how encounter rates depend on key phenotypic and environmental variables. Encounter kernels also provide physically grounded estimates for parameters that are used in ecological models of microbial populations. We illustrate this encounter-oriented perspective on microbial interactions by reviewing traditional and recently identified kernels describing encounters between microorganisms and between microorganisms and resources in aquatic systems.

Correlated Fluctuations of Structural Indicators Close to the Liquid-Liquid Transition in Supercooled Water.

Multiple numerical studies have unambiguously shown the existence of a liquid-liquid critical point in supercooled states for different numerical models of water, and various structural indicators have been put forward to describe the transformation associated with this phase transition. Here we analyze numerical simulations of near-critical supercooled water to compare the behavior of several of such indicators with critical density fluctuations. We show that close to the critical point most indicators are strongly correlated to density, and some of them even display identical distributions of fluctuations. These indicators probe the exact same free energy landscape, therefore providing a thermodynamic description of critical supercooled water which is identical to that provided by the density order parameter. This implies that close to the critical point, there is a tight coupling between many, only apparently distinct, structural degrees of freedom.

Structure of High-Pressure Supercooled and Glassy Water.

We numerically investigate the structure of deep supercooled and glassy water under pressure, covering the range of densities corresponding to the experimentally produced high- and very-high-density amorphous phases. At T=188 K, a continuous increase in density is observed on varying pressure from 2.5 to 13 kbar, with no signs of first-order transitions. Exploiting a recently proposed approach to the analysis of the radial distribution function-based on topological properties of the hydrogen-bond network-we are able to identify well-defined local geometries that involve pairs of molecules separated by multiple hydrogen bonds, specific to the high- and very-high-density structures.

Structural and topological changes across the liquid-liquid transition in water.

It has recently been shown that the TIP4P/Ice model of water can be studied numerically in metastable equilibrium at and below its liquid-liquid critical temperature. We report here simulations along a subcritical isotherm, for which two liquid states with the same pressure and temperature but different density can be equilibrated. This allows for a clear visualization of the structural changes taking place across the transition. We specifically focus on how the topological properties of the H-bond network change across the liquid-liquid transition. Our results demonstrate that the structure of the high-density liquid, characterized by the existence of interstitial molecules and commonly explained in terms of the collapse of the second neighbor shell, actually originates from the folding back of long rings, bringing pairs of molecules separated by several hydrogen-bonds close by in space.