Spontaneous liquid-liquid phase separation of water

Yagasaki, Takuma; Matsumoto, Masakazu; Tanaka, Hideki

doi:10.1103/physreve.89.020301

Cited by 85 publications

(131 citation statements)

References 34 publications

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“…The isotherms are obtained by extensive canonical ensemble [constant number of molecules, volume, and temperature (NVT)] molecular dynamics (MD) simulations of the TIP4P model of N = 720, 900, and 1,080 water molecules encapsulated in model single-walled carbon nanotubes (see Methods for details). Note that direct calculations of isotherms have provided compelling evidence of the liquid-liquid phase transition in models of supercooled water (16)(17)(18). Plotted in Fig.…”

Section: Resultsmentioning

confidence: 99%

Solid−liquid critical behavior of water in nanopores

Mochizuki

Koga

2015

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

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Nanoconfined liquid water can transform into low-dimensional ices whose crystalline structures are dissimilar to any bulk ices and whose melting point may significantly rise with reducing the pore size, as revealed by computer simulation and confirmed by experiment. One of the intriguing, and as yet unresolved, questions concerns the observation that the liquid water may transform into a low-dimensional ice either via a first-order phase change or without any discontinuity in thermodynamic and dynamic properties, which suggests the existence of solid−liquid critical points in this class of nanoconfined systems. Here we explore the phase behavior of a model of water in carbon nanotubes in the temperature−pressure− diameter space by molecular dynamics simulation and provide unambiguous evidence to support solid−liquid critical phenomena of nanoconfined water. Solid−liquid first-order phase boundaries are determined by tracing spontaneous phase separation at various temperatures. All of the boundaries eventually cease to exist at the critical points and there appear loci of response function maxima, or the Widom lines, extending to the supercritical region. The finite-size scaling analysis of the density distribution supports the presence of both first-order and continuous phase changes between solid and liquid. At around the Widom line, there are microscopic domains of two phases, and continuous solid−liquid phase changes occur in such a way that the domains of one phase grow and those of the other evanesce as the thermodynamic state departs from the Widom line.T he possibility of the solid-liquid critical point has been reported by computer simulation studies of various systems in quasi-one, quasi-two, and three dimensions that exhibit both continuous and discontinuous changes in thermodynamic functions and other order parameters (1-7). However, the idea that a solid-liquid phase boundary never terminates at the critical point is still commonly accepted as a law of nature, largely because of the famous symmetry argument (8, 9) together with the lack of experimental observations. Furthermore, critical phenomena in quasi-1D systems are often considered impossible from a different point of view; that is, to begin with, there is no first-order phase transition in 1D systems as proved for solvable models (10) or shown by the phenomenological argument (9). Therefore, a thorough investigation is much needed to support or reject the possibility of the solid-liquid critical point. We examine the phase behavior of a model system of water confined in a quasi-1D nanopore (1,(11)(12)(13)(14)(15) and provide evidence to support the existence of first-order phase transitions and solid-liquid critical points. Results and DiscussionsFirst, we explore possible solid-liquid critical points of the confined water by calculating isotherms in the "pressure-volume" plane, where the pressure is actually P zz , a component of pressure tensor along the tube axis, or simply the axial pressure, and the volume is ℓ z , the length of simulatio...

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Section: Resultsmentioning

confidence: 99%

Solid−liquid critical behavior of water in nanopores

Mochizuki

Koga

2015

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

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“…45 The important distinction is that the relaxation pathway in water is one which utilizes the strong interaction of the hydrogen bond, which in the case of the experiments presented here exhibit enhanced polarization 67,68 . When one expands the number of molecules involved in the relaxation process a length scale emerges whereby the local and collective modes can effectively decouple from each other -the mesoscale 24,69,70 . In the presence of the field gradient this decoupling is enhanced and essentially results in transiently isolated molecular populations within the liquid.…”

Section: Implications Of An Extended Vibrational Energy Modementioning

confidence: 99%

Non-equilibrium thermodynamics and collective vibrational modes of liquid water in an inhomogeneous electric field

Wexler¹,

Drusová²,

Woisetschläger

et al. 2016

Phys. Chem. Chem. Phys.

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“…Equation (19) describes the crossover of the heat capacity between two limits. In the limit x → 0 one recovers the expression for the heat capacity of pure water, diverging at the critical point as…”

Section: A Suppression Of Heat Capacity Anomaly In Aqueous Solutionsmentioning

confidence: 99%

“…This hypothesized liquid-liquid coexistence, terminated by a critical point, is not directly accessible to bulk-water experiments because it is presumably located a few degrees below the line of homogeneous nucleation of ice [2,4,5]. Fresh approaches to resolving the question of the existence of water's polyamorphism are especially desirable in view of conflicting reports on simulations in water-like models [6][7][8][9][10][11][12][13][14][15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

Behavior of supercooled aqueous solutions stemming from hidden liquid–liquid transition in water

Biddle

Holten

Анисимов

2014

The Journal of Chemical Physics

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A popular hypothesis that explains the anomalies of supercooled water is the existence of a metastable liquid-liquid transition hidden below the line of homogeneous nucleation. If this transition exists and if it is terminated by a critical point, the addition of a solute should generate a line of liquid-liquid critical points emanating from the critical point of pure metastable water. We have analyzed thermodynamic consequences of this scenario. In particular, we consider the behavior of two systems, H2O-NaCl and H2O-glycerol. We find the behavior of the heat capacity in supercooled aqueous solutions of NaCl, as reported by Archer and Carter, to be consistent with the presence of the metastable liquid-liquid transition. We elucidate the non-conserved nature of the order parameter (extent of "reaction" between two alternative structures of water) and the consequences of its coupling with conserved properties (density and concentration). We also show how the shape of the critical line in a solution controls the difference in concentration of the coexisting liquid phases.

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Spontaneous liquid-liquid phase separation of water

Cited by 85 publications

References 34 publications

Solid−liquid critical behavior of water in nanopores

Solid−liquid critical behavior of water in nanopores

Non-equilibrium thermodynamics and collective vibrational modes of liquid water in an inhomogeneous electric field

Behavior of supercooled aqueous solutions stemming from hidden liquid–liquid transition in water

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