Freezing of hard spheres confined in narrow cylindrical pores

Gordillo, M. C.; Martínez–Haya, Bruno; Romero-Enrique, J. M.

doi:10.1063/1.2358135

Cited by 31 publications

(29 citation statements)

References 21 publications

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“…Using hard body molecular models and hard confining walls it is possible to study purely the geometrical packing effects as the energetic effect are not included in these models. In this regard much attention has been paid to understand the structure and the phase behaviour of several confined systems such as the ordering of hard spheres in narrow cylindrical pore [8,9,10] and slit pores [11] and the helical packing of soft spheres in nanotubes [12,13]. The rapid development of the X-ray techniques makes also possible to study extremely confined fluids, where the particles are confined between two hard walls with thickness just slightly higher than the diameter of the particle [14].…”

Section: Introductionmentioning

confidence: 99%

Structural properties of hard disks in a narrow tube

Varga¹,

Balló²,

Gurin³

2011

J. Stat. Mech.

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Abstract. Positional ordering of a two-dimensional fluid of hard disks is examined in such narrow tubes where only the nearest-neighbor interactions take place. Using the exact transfer-matrix method the transverse and longitudinal pressure components and the correlation function are determined numerically. Fluid-solid phase transition does not occur even in the widest tube, where the method just loses its exactness, but the appearance of the dramatic change in the equation of state and the longitudinal correlation function shows that the system undergoes a structural change from a fluid to a solid-like order. The pressure components show that the collisions are dominantly longitudinal at low densities, while they are transverse in the vicinity of close packing density. The transverse correlation function shows that the size of solid-like domains grows exponentially with increasing pressure and the correlation length diverges at close packing. It is managed to find an analytically solvable model by expanding the contact distance up to first order. The approximate model, which corresponds to the system of hard parallel rhombuses, behaves very similarly to the system of hard disks.

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Section: Introductionmentioning

confidence: 99%

Structural properties of hard disks in a narrow tube

Varga¹,

Balló²,

Gurin³

2011

J. Stat. Mech.

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“…water | solid−liquid critical point | carbon nanotube | ice | 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)(2)(3)(4)(5)(6)(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.…”

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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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“…Later, theoretical quantification for hard-sphere fluids in the very narrow pore was established. 21 In recent years, Gordillo et al 15 observed the onset of freezing shown by a sharp change of the density at certain radii of pores via the same NPT MC method and elucidated that the cause of this behavior is microstructural transformation. With effects of the attractive potential, Koga and Tanaka 7 studied Lennard-Jones ͑LJ͒ confined fluids analogous to argon atoms trapped in single-wall CNT via molecular dynamics ͑MD͒ method.…”

Section: Introductionmentioning

confidence: 99%

“…The former reason is based on several numerical evidences on the existence of the fluidsolid phase transition in both for bulk [11][12][13][14] or confined systems 15 with the absence of attractive interactions. The latter provides the system under effects of dominant influence of entropy, thus leading one to focus on the relation of the phase transition and the structure of confined particles with varying pore sizes.…”

Section: Introductionmentioning

confidence: 99%

Characterization of fluid-solid phase transition of hard-sphere fluids in cylindrical pore via molecular dynamics simulation

Huang

Kwak

Singh

2009

The Journal of Chemical Physics

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Articles you may be interested inThe isotropic-nematic phase transition of tangent hard-sphere chain fluids-Pure components J. Chem. Phys. 139, 034505 (2013) Equation of state and structure of hard-sphere fluids confined in a cylindrical hard pore were investigated at the vicinity of fluid-solid transition via molecular dynamics simulation. By constructing artificial closed-packed structures in a cylindrical pore, we explicitly capture the fluid-solid phase transition and coexistence for the pore diameters from 2.17 to 15. There exist some midpore sizes, where the phase coexistence might not exist or not clearly be observable. We found that the axial pressure including coexistence follows oscillatory behavior in different pore sizes; while the pressure tends to decrease toward the bulk value with increasing pore size, the dependence of the varying pressure on the pore size is nonmonotonic due to the substantial change of the alignment of the molecules. The freezing and melting densities corresponding to various pore sizes, which are always found to be lower than those of the bulk system, were accurately obtained with respect to the axial pressure.

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Freezing of hard spheres confined in narrow cylindrical pores

Abstract: Finite-size effects in the microscopic structure of a hard-sphere fluid in a narrow cylindrical pore

Cited by 31 publications

References 21 publications

Structural properties of hard disks in a narrow tube

Structural properties of hard disks in a narrow tube

Solid−liquid critical behavior of water in nanopores

Characterization of fluid-solid phase transition of hard-sphere fluids in cylindrical pore via molecular dynamics simulation

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