The physics of empty liquids: from patchy particles to water

Russo, John; Leoni, F.; Martelli, Fausto; Sciortino, Francesco

doi:10.1088/1361-6633/ac42d9

Cited by 30 publications

(37 citation statements)

References 222 publications

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salient feature of liquid water is the anomalous behaviour of its thermodynamic response functions upon cooling, the most famous being the density maximum at ambient pressure [1][2][3][4][5][6] . In an effort to explain the origin of water's thermodynamic anomalies, enhanced in supercooled states, Poole et al suggested the presence of a first-order liquid-liquid phase transition (LLPT) line in the supercooled region of the pressure-temperature (P-T) phase diagram 7 .

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confidence: 99%

Topological nature of the liquid–liquid phase transition in tetrahedral liquids

2022

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The first-order phase transition between two tetrahedral networks of different density—introduced as a hypothesis to account for the anomalous behaviour of certain thermodynamic properties of deeply supercooled water—has received strong support from a growing body of work in recent years. Here we show that this liquid–liquid phase transition in tetrahedral networks can be described as a transition between an unentangled, low-density liquid and an entangled, high-density liquid, the latter containing an ensemble of topologically complex motifs. We first reveal this distinction in a rationally designed colloidal analogue of water. We show that this colloidal water model displays the well-known water thermodynamic anomalies as well as a liquid–liquid critical point. We then investigate water, employing two widely used molecular models, to demonstrate that there is also a clear topological distinction between its two supercooled liquid networks, thereby establishing the generality of this observation, which might have far-reaching implications for understanding liquid–liquid phase transitions in tetrahedral liquids.

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Topological nature of the liquid–liquid phase transition in tetrahedral liquids

2022

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“…Thus, at the triple point, the packing fraction ρv vdW with v vdW standing for the so-called van der Waals volumeis ∼38% for water and ∼60% for neon, argon, xenon, or krypton. The latter four are known to pertain to a broad class of liquids often referred to as “simple liquids.” Liquid water can be losely packed relative to simple liquids and, as such, is considered a representative member of the class of “empty liquids,” as patchy colloids are too …”

Section: Water As a One-component Fluidmentioning

confidence: 99%

“…Liquid water can be losely packed relative to simple liquids and, as such, is considered a representative member of the class of "empty liquids," as patchy colloids are too. 20 Simple liquids are understood from the classical interpretation of van der Waals theory due to H. C. Longhet-Higgins and B. Widom, which stresses that the packing effects inherent to the hard part of the pair potential largely determine the liquid's structure while attractive forces enter as a perturbation. This picture is, however, incapable to sustain a ρv vdW value as low as the one of liquid water.…”

Section: Water As a One-component Fluidmentioning

confidence: 99%

“…It is widely recognized that van der Waals theory breaks down for hydrogen-bonded liquids such as water or alcohols, and while standard theories for molecular association indeed work for alcohols and can even lead to arbitrarily low ρv vdW values for the liquid phase, they are still unable to reproduce the unusual thermodynamics of water. 20 Certainly, the existing theories of association do not capture the special features of hydrogen bonding in water, which is known to generate "ice-like" local structures with a high volume per particle that is incompatible with close packing. A key underlying feature is the existence of an "optimal network forming density" preserving every ice-like structure.…”

Section: Water As a One-component Fluidmentioning

confidence: 99%

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Water’s Unusual Thermodynamics in the Realm of Physical Chemistry

Cerdeiriña

2022

J. Phys. Chem. B

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While it is known since the early work by Edsall, Frank and Evans, Kauzmann, and others that the thermodynamics of solvation of nonpolar solutes in water is unusual and has implications for the thermodynamics of protein folding, only recently have its connections with the unusual temperature dependence of the density of solvent water been illuminated. Such density behavior is, in turn, one of the manifestations of a nonstandard thermodynamic pattern contemplating a second, liquid–liquid critical point at conditions of temperature and pressure at which water exists as a deeply supercooled liquid. Recent experimental and computational work unambiguously points toward the existence of such a critical point, thereby providing concrete answers to the questions posed by the 1976 pioneering experiments by Speedy and Angell and the associated “liquid–liquid transition hypothesis” posited in 1992 by Stanley and co-workers. Challenges of this phenomenology to the branch of Statistical Mechanics remain.

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“…This makes the assembly particularly difficult for the isotropic and short-range potentials that typically govern colloidal particles, and which tend to favour close-packed structures. To overcome this problem, one of the most promising approaches has been to use anisotropic interactions, 9 and in particular colloidal particles with tetrahedrally arranged bonding sites. These particles are termed Patchy Particles (Fig.…”

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confidence: 99%