Communication: Re-entrant limits of stability of the liquid phase and the Speedy scenario in colloidal model systems

Rovigatti, Lorenzo; Bianco, Valentino; Tavares, J. M.; Sciortino, Francesco

doi:10.1063/1.4974830

Cited by 26 publications

(30 citation statements)

References 64 publications

(66 reference statements)

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“…As with previous models of patchy colloids 14,15,36 , competition between different modes of attraction results in anomalous phase behavior. These previous patchy colloid models required two types of patches (bi-functional) to obtain competing energy scales.…”

Section: Iv: Discussion and Summarysupporting

confidence: 74%

“…The ratio RAΨ defined in Eq. (36) will then quantify the strength of AA attractions in relation to AΨ attractions (36) To solve for the bonding fractions XA we combine Eqns. (18), (20) and (22) A quantity which describes the competition between AA and AΨ attractions is Θ which is defined as the ratio (40) For Θ > 1 AA interactions dominate while for Θ <1 AΨ interactions dominate.…”

Section: D) Competitive Colloids With λ Equivalent Patchesmentioning

confidence: 99%

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A theory for the effect of patch/non-patch attractions on the self-assembly of patchy colloids

Marshall

2017

Soft Matter

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In this paper, we develop a thermodynamic perturbation theory to describe the selfassembly of patchy colloids which exhibit both patch-patch attractions as well as patch / non-patch attractions. That is, patches attract other patches as well as the no patch region (we call this region Ψ). In general, the patch-patch and patch-Ψ attractions operate on different energy scales allowing for a competition between different modes of attraction. This competition may result in anomalous thermodynamic properties. As an application, we tune the patch parameters to reproduce the liquid density (suitably scaled) maximum of water. It is then shown that the liquid branch of the colloids phase diagram has liquid densities consistent with both saturated and super-cooled liquid water. Finally, it is shown that the colloids reproduce water's anomalous minimum in isothermal compressibility and negative volume expansivity.

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Section: Iv: Discussion and Summarysupporting

confidence: 74%

Section: D) Competitive Colloids With λ Equivalent Patchesmentioning

confidence: 99%

A theory for the effect of patch/non-patch attractions on the self-assembly of patchy colloids

Marshall

2017

Soft Matter

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“…The stability limit is the limiting set of thermodynamic conditions at which a metastable phase collapses, effectively defining the boundary for metastable phase existence. In the special case of the mean field, this will coincide with the spinodal line 64 (see below). The stability limit line does not have any special derivative properties (except when it coincides with the spinodal), and so we can write, in general, an expression for the gradient in the PT projection of any line by expanding the differential of P as a function of V and T,…”

Section: A the Stability Limitmentioning

confidence: 90%

The interactions between thermodynamic anomalies

Fijan

Wilson

2019

The Journal of Chemical Physics

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The origin of and interactions between key thermodynamic anomalies are derived and analyzed, as are the interactions with the stability (or cavitation) limits. The conditions for interaction are derived from the underlying thermodynamic relations rather than using the morecommonly applied Taylor expansion method. As a result, we derive a general set of equations that govern the interactions between different lines of thermodynamic anomalies using standard manipulation of thermodynamic equations. The validity of the derivations is investigated by comparing them to numerical simulation data and previous Taylor expansion-based results. Simulations are performed using a modified Stillinger-Weber potential in which the balance of the two-and three-body interactions is varied and which serves to highlight the relationships between the various anomalies. The deeply supercooled regime is explored by employing replica exchange methods. The behavior of the anomalies is considered in terms of previously constructed thermodynamic "scenarios." Based on the newly uncovered interaction schemes, we propose a classification strategy for the thermodynamic anomalies (as first-or second-order) which could be extended to additional related anomalies.

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“…If the spinodal traces back to positive P, the liquid becomes unstable to gas-like fluctuations both on heating and on cooling (40). Despite the difficulty of imagining a liquid that would vaporize on cooling, Speedy's scenario is thermodynamically consistent and it has been recently observed in one-component models of patchy colloids (24,25). In these models the reentrance is provided by closed-loop phase diagrams ( Fig.…”

Section: Liquid Watermentioning

confidence: 91%

Supercooled and glassy water: Metastable liquid(s), amorphous solid(s), and a no-man’s land

Handle

Loerting

Sciortino

2017

Proc. Natl. Acad. Sci. U.S.A.

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119

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We review the recent research on supercooled and glassy water, focusing on the possible origins of its complex behavior. We stress the central role played by the strong directionality of the water–water interaction and by the competition between local energy, local entropy, and local density. In this context we discuss the phenomenon of polyamorphism (i.e., the existence of more than one disordered solid state), emphasizing both the role of the preparation protocols and the transformation between the different disordered ices. Finally, we present the ongoing debate on the possibility of linking polyamorphism with a liquid–liquid transition that could take place in the no-man’s land, the temperature–pressure window in which homogeneous nucleation prevents the investigation of water in its metastable liquid form.

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Communication: Re-entrant limits of stability of the liquid phase and the Speedy scenario in colloidal model systems

Abstract: Articles you may be interested in

Cited by 26 publications

References 64 publications

A theory for the effect of patch/non-patch attractions on the self-assembly of patchy colloids

A theory for the effect of patch/non-patch attractions on the self-assembly of patchy colloids

The interactions between thermodynamic anomalies

Supercooled and glassy water: Metastable liquid(s), amorphous solid(s), and a no-man’s land

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