Erik Lascaris

Water: A Tale of Two Liquids

Water is the most abundant liquid on earth and also the substance with the largest number of anomalies in its properties. It is a prerequisite for life and as such a most important subject of current research in chemical physics and physical chemistry. In spite of its simplicity as a liquid, it has an enormously rich phase diagram where different types of ices, amorphous phases, and anomalies disclose a path that points to unique thermodynamics of its supercooled liquid state that still hides many unraveled secrets. In this review we describe the behavior of water in the regime from ambient conditions to the deeply supercooled region. The review describes simulations and experiments on this anomalous liquid. Several scenarios have been proposed to explain the anomalous properties that become strongly enhanced in the supercooled region. Among those, the second critical-point scenario has been investigated extensively, and at present most experimental evidence point to this scenario. Starting from very low temperatures, a coexistence line between a high-density amorphous phase and a low-density amorphous phase would continue in a coexistence line between a high-density and a low-density liquid phase terminating in a liquid–liquid critical point, LLCP. On approaching this LLCP from the one-phase region, a crossover in thermodynamics and dynamics can be found. This is discussed based on a picture of a temperature-dependent balance between a high-density liquid and a low-density liquid favored by, respectively, entropy and enthalpy, leading to a consistent picture of the thermodynamics of bulk water. Ice nucleation is also discussed, since this is what severely impedes experimental investigation of the vicinity of the proposed LLCP. Experimental investigation of stretched water, i.e., water at negative pressure, gives access to a different regime of the complex water diagram. Different ways to inhibit crystallization through confinement and aqueous solutions are discussed through results from experiments and simulations using the most sophisticated and advanced techniques. These findings represent tiles of a global picture that still needs to be completed. Some of the possible experimental lines of research that are essential to complete this picture are explored.

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

The liquid-liquid critical point scenario of water hypothesizes the existence of two metastable liquid phases--low-density liquid (LDL) and high-density liquid (HDL)--deep within the supercooled region. The hypothesis originates from computer simulations of the ST2 water model, but the stability of the LDL phase with respect to the crystal is still being debated. We simulate supercooled ST2 water at constant pressure, constant temperature, and constant number of molecules N for N ≤ 729 and times up to 1 μs. We observe clear differences between the two liquids, both structural and dynamical. Using several methods, including finite-size scaling, we confirm the presence of a liquid-liquid phase transition ending in a critical point. We find that the LDL is stable with respect to the crystal in 98% of our runs (we perform 372 runs for LDL or LDL-like states), and in 100% of our runs for the two largest system sizes (N = 512 and 729, for which we perform 136 runs for LDL or LDL-like states). In all these runs, tiny crystallites grow and then melt within 1 μs. Only for N ≤ 343 we observe six events (over 236 runs for LDL or LDL-like states) of spontaneous crystallization after crystallites reach an estimated critical size of about 70 ± 10 molecules.

Diffusivity and short-time dynamics in two models of silica

We discuss the dynamic behavior of two silica models, the BKS model (by van Beest, Kramer, and van Santen) and the WAC model (by Woodcock, Angell, and Cheeseman). Although BKS is considered the more realistic model for liquid silica, the WAC model has the unique property that it is very close to having a liquid-liquid critical point (LLCP), and this makes it particularly useful in studying the dynamics of models that do have a LLCP. We find that the diffusivity is a good indicator of how close a liquid is to criticality--the Si diffusivity shows a jump of 3-4 orders of magnitude when the pressure is reduced, which may be interpreted as an abrupt (though not first-order) transition from a high-density liquid state to a low-density liquid state. We show that this transition is captured by the Adam-Gibbs relation, which also allows us to estimate the configurational entropy of the system.

Liquid–liquid phase transition in an ionic model of silica

Recent equation of state calculations [E. Lascaris, Phys. Rev. Lett. 116, 125701 (2016)] for an ionic model of silica suggest that it undergoes a density-driven, liquid-liquid phase transition (LLPT) similar to the controversial transition hypothesized to exist in deeply supercooled water. Here, we perform extensive free energy calculations to scrutinize the models low-temperature phase behavior and confirm the existence of a first-order phase transition between two liquids with identical compositions but different densities. The low-density liquid (LDL) exhibits tetrahedral order, which is partially disrupted in the high-density liquid (HDL) by the intrusion of additional particles into the primary neighbor shell. Histogram reweighting methods are applied to locate conditions of HDL-LDL coexistence and the liquid spinodals that bound the two-phase region. Spontaneous liquid-liquid phase separation is also observed directly in large-scale molecular dynamics simulations performed inside the predicted two-phase region. Given its clear LLPT, we anticipate that this model may serve as a paradigm for understanding whether similar transitions occur in water and other tetrahedral liquids.

Tunable Liquid-Liquid Critical Point in an Ionic Model of Silica.

Recently, it was shown that the Woodcock-Angell-Cheeseman model for liquid silica [L. V. Woodcock, C. A. Angell, and P. Cheeseman, J. Chem. Phys. 65, 1565 (1976)] is remarkably close to having a liquid-liquid critical point (LLCP). We demonstrate that increasing the ion charge separates the global maxima of the response functions, while reducing the charge smoothly merges them into a LLCP, a phenomenon that might be experimentally observable with charged colloids. An analysis of the Si and O coordination numbers suggests that a sufficiently low Si/O coordination number ratio is needed to attain a LLCP.

The HiSPARC Project; Science, Technology and Education

HiSPARC is a project where high school teachers and students work together to study cosmic rays. The combination of hands‐on experience and truly participating in a scientific collaboration opens the eyes of many high‐school students for the scientific and technological world surrounding us. In this way HiSPARC helps to achieve the targets set in Lisbon 2000 to increase the number of students completing a scientific or technical study, in 2010 by 15%. This paper gives an overview of the project with the emphasis on its implementation in the Dutch educational system.