Metastable liquid-liquid coexistence and density anomalies in a core-softened fluid

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H. M. Gibson and N. B. Wilding
Department of Physics, University of Bath, Bath BA2 7AY, United Kingdom

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Received 28 February 2006; published 21 June 2006; publisher error corrected 29 June 2006

Linearlysloped or "ramp" potentials belong to a class of core-softenedmodels which possess a liquid-liquid critical point (LLCP) in additionto the usual liquid-gas critical point. Furthermore, they exhibit thermodynamicanomalies in their density and compressibility, the nature of whichmay be akin to those occurring in water. Previous simulationstudies of ramp potentials have focused on just one functionalform, for which the LLCP is thermodynamically stable. In thiswork we construct a series of ramp potentials, which interpolatebetween this previously studied form and a ramp-based approximation tothe Lennard-Jones (LJ) potential. By means of Monte Carlo simulation,we locate the LLCP, the first order high density liquid(HDL)–low density liquid (LDL) coexistence line, and the line ofdensity maxima for a selection of potentials in the series.We observe that as the LJ limit is approached, theLLCP becomes metastable with respect to freezing into a hexagonalclose packed crystalline solid. The qualitative nature of the phasebehavior in this regime shows a remarkable resemblance to thatseen in simulation studies of accurate water models. Specifically, thedensity of the liquid phase exceeds that of the solid;the gradient of the metastable LDL-HDL line is negative inthe pressure (p)-temperature (T) plane; while the line of densitymaxima in the p-T plane has a shape similar tothat seen in water and extends into the stable liquidregion of the phase diagram. As such, our results lendweight to the "second critical point" hypothesis as an explanationfor the anomalous behavior of water.

URL:	http://link.aps.org/doi/10.1103/PhysRevE.73.061507
DOI:	10.1103/PhysRevE.73.061507
PACS:	64.70.Ja; 64.60.My; 64.60.Fr 64.70.Ja Liquid–liquid transitions 64.60.My Metastable phases 64.60.Fr Equilibrium properties near critical points, critical exponents YEAR: 2006
KEYWORDS:	liquid-liquid transformations, critical points, Monte Carlo methods, liquid-vapour transformations, Lennard-Jones potential, phase diagrams

REFERENCES (46)

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D. Hohl and R. O. Jones, Phys. Rev. B 45, 8995 (1992).
M. van Thiel and F. H. Ree, Phys. Rev. B 48, 3591 (1993).
J. S. Tse and D. D. Klug, Phys. Rev. B 59, 34 (1999).
Phys. Rev. E 48, 3799 (1993).
M. Yamada, S. Mossa, H. E. Stanley, and F. Sciortino, Phys. Rev. Lett. 88, 195701 (2002).
N. Giovambattista, H. E. Stanley, and F. Sciortino, Phys. Rev. Lett. 94, 107803 (2005).
P. C. Hemmer and G. Stell, Phys. Rev. Lett. 24, 1284 (1970);

J. Chem. Phys. 65, 2161 (1976)

65, 2172 (1976)

ibid. 67, 420 (1977)

B. Pellicane, G. Pellicane, and G. Malescio, J. Chem. Phys. 120, 8671 (2004).
D. Quigley and M. I. J. Probert, Phys. Rev. E 71, 065701(R) (2005);

72, 061202 (2005)

G. Malescio, G. Franzese, A. Skibinsky, S. V. Buldyrev, and H. E. Stanley, Phys. Rev. E 71, 061504 (2005).
A. Barros de Oliveira, T. Colla, and M. C. Barbosa, J. Chem. Phys. 124, 084505 (2006).
M. R. Sadr-Lahijany, A. Scala, S. V. Buldyrev, and H. E. Stanley, Phys. Rev. Lett. 81, 4895 (1998).
N. B. Wilding and J. E. Magee, Phys. Rev. E 66, 031509 (2002).
E. A. Jagla, Phys. Rev. E 63, 061501 (2001);

J. Chem. Phys. 111, 8980 (1999)

P. Kumar, S. V. Buldyrev, F. Sciortino, E. Zaccarelli, and H. E. Stanley, Phys. Rev. E 72, 021501 (2005).
Z. Yan, S. V. Buldyrev, N. Giovambattista, P. G. Debenedetti, and H. E. Stanley, Phys. Rev. E 73, 051204 (2006);

Phys. Rev. Lett. 95, 130604 (2005)

G. A. Vliegenthart and H. N. W. Lekkerkerker, J. Chem. Phys. 112, 5364 (2000).
M. G. Noro and D. Frenkel, J. Chem. Phys. 113, 2941 (2000).
B. A. Berg and T. Neuhaus, Phys. Rev. Lett. 68, 9 (1992).
A. M. Ferrenberg and R. H. Swendsen, Phys. Rev. Lett. 61, 2635 (1988);

63, 1195 (1989)

N. B. Wilding, Phys. Rev. E 52, 602 (1995).
A. Scala, F. W. Starr, E. La Nave, H. E. Stanley, and F. Sciortino, Phys. Rev. E 62, 8016 (2000).
P. G. Debenedetti and M. C. D'Antonio, J. Chem. Phys. 84, 3339 (1986).
V. B. Henriques and M. C. Barbosa, Phys. Rev. E 71, 031504 (2005);
F. Sciortino, E. La Nave, and P. Tartaglia, Phys. Rev. Lett. 91, 155701 (2003).
G. Franzese, M. I. Marques, and H. E. Stanley, Phys. Rev. E 67, 011103 (2003);

J. Chem. Phys. 111, 2647 (1999)

ibid. 105, 658 (1996)

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Erratum

Publisher's Note: Metastable liquid-liquid coexistence and density anomalies in a core-softened fluid [Phys. Rev. E 73, 061507 (2006)]
H. M. Gibson and N. B. Wilding
Phys. Rev. E 74, 019903 (E) (2006)