Erratum: On the nature of the tensile instability in metastable liquids and its relationship to density anomalies [J. Chem. Phys. <b>8</b>
                  <b>4</b>, 3339 (1986)]

Debenedetti, Pablo G.; D’Antonio, Michael C.

doi:10.1063/1.451874

Cited by 8 publications

(9 citation statements)

References 6 publications

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“…However, it remains unclear why shoulder potentials exhibit a LL transition, but no density anomaly, while ramp potentials exhibit both. As regards the locus of the line, thermodynamic considerations limit the number of ways in which it can terminate [38,39]; specifically it must either intersect a spinodal or transform smoothly into a line of density minima. For the family of ramp potentials studied in the present work, the line of density anomalies was always found to approach the LLCP at their high pressure end.…”

Section: Discussionmentioning

confidence: 99%

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

2006

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Linearly sloped or "ramp" potentials belong to a class of core-softened models which possess a liquid-liquid critical point (LLCP) in addition to the usual liquid-gas critical point. Furthermore, they exhibit thermodynamic anomalies in their density and compressibility, the nature of which may be akin to those occurring in water. Previous simulation studies of ramp potentials have focused on just one functional form, for which the LLCP is thermodynamically stable. In this work we construct a series of ramp potentials, which interpolate between this previously studied form and a ramp-based approximation to the 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 of density maxima for a selection of potentials in the series. We observe that as the LJ limit is approached, the LLCP becomes metastable with respect to freezing into a hexagonal close packed crystalline solid. The qualitative nature of the phase behavior in this regime shows a remarkable resemblance to that seen in simulation studies of accurate water models. Specifically, the density of the liquid phase exceeds that of the solid; the gradient of the metastable LDL-HDL line is negative in the pressure (p)-temperature (T) plane; while the line of density maxima in the p-T plane has a shape similar to that seen in water and extends into the stable liquid region of the phase diagram. As such, our results lend weight to the "second critical point" hypothesis as an explanation for the anomalous behavior of water.

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Section: Discussionmentioning

confidence: 99%

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

2006

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“…After this point the line becomes negatively sloped and joins continuously the stability limit with respect to the ordered ice phase. The TMD locus intersects the limit of stability in its minimum in the T-P plane, according to the predictions of Speedy and Debenedetti [37][38][39][40][41][42][43], based on thermodynamic consistency arguments. In fact, the TMD locus causes the liquid limit of stability line to retrace, giving rise to a tensile strength maximum and to a continuous boundary.…”

Section: B Tmd Locus and Stability Limitsmentioning

confidence: 99%

Two-dimensional lattice-fluid model with waterlike anomalies

et al. 2004

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We investigate a lattice-fluid model defined on a two-dimensional triangular lattice, with the aim of reproducing qualitatively some anomalous properties of water. Model molecules are of the "Mercedes Benz" type, i.e., they possess a D3 (equilateral triangle) symmetry, with three bonding arms. Bond formation depends both on orientation and local density. We work out phase diagrams, response functions, and stability limits for the liquid phase, making use of a generalized first order approximation on a triangle cluster, whose accuracy is verified, in some cases, by Monte Carlo simulations. The phase diagram displays one ordered (solid) phase which is less dense than the liquid one. At fixed pressure the liquid phase response functions show the typical anomalous behavior observed in liquid water, while, in the supercooled region, a reentrant spinodal is observed.

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“…If the negative slope would extend to large negative pressures (SLC scenario), it would meet the vapor-liquid spinodal. In such a case, thermodynamic consistency requires 24 that the spinodal would retrace at the intersection point. On the other hand, the TMD could change its slope leading to a nose-shaped function (LLCP and SF scenarios).…”

Section: Introductionmentioning

confidence: 99%

A comprehensive scenario of the thermodynamic anomalies of water using the TIP4P/2005 model

Gonzalez

Valeriani

Caupin

et al. 2016

The Journal of Chemical Physics

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The striking behavior of water has deserved it to be referred to as an "anomalous" liquid. The water anomalies are greatly amplified in metastable (supercooled and/or stretched) regions. This makes difficult a complete experimental description since, beyond certain limits, the metastable phase necessarily transforms into the stable one. Theoretical interpretation of the water anomalies could then be based on simulation results of well validated water models. But the analysis of the simulations has not yet reached a consensus. In particular, one of the most popular theoretical scenarios-involving the existence of a liquid-liquid critical point (LLCP)-is disputed by several authors. In this work, we propose to use a number of exact thermodynamic relations which may shed light on this issue. Interestingly, these relations may be tested in a region of the phase diagram which is outside the LLCP thus avoiding the problems associated to the coexistence region. The central property connected to other water anomalies is the locus of temperatures at which the density along isobars attain a maximum (TMD line) or a minimum (TmD). We have performed computer simulations to evaluate the TMD and TmD for a successful water model, namely, TIP4P/2005. We have also evaluated the vapor-liquid (VL) spinodal in the region of large negative pressures. The shape of these curves and their connection to the extrema of some response functions, in particular the isothermal compressibility and heat capacity at constant pressure, provides very useful information which may help to elucidate the validity of the theoretical proposals. In this way, we are able to present for the first time a comprehensive scenario of the thermodynamic water anomalies for TIP4P/2005 and their relation to the vapor-liquid spinodal. The overall picture shows a remarkable similarity with the corresponding one for the ST2 water model, for which the existence of a LLCP has been demonstrated in recent years. It also provides a hint as to where the long-sought for extrema in response functions might become accessible to experiments.

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Erratum: On the nature of the tensile instability in metastable liquids and its relationship to density anomalies [J. Chem. Phys. 8 4, 3339 (1986)]

Abstract: Erratum: Cluster formation of hydrogen cyanide in solid and liquid CCl4 matrices [J.On the nature of the tensile instability in metastable liquids and its relationship to density anomalies

Cited by 8 publications

References 6 publications

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

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

Two-dimensional lattice-fluid model with waterlike anomalies

A comprehensive scenario of the thermodynamic anomalies of water using the TIP4P/2005 model

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