Spinodal curve of some supercooled liquids

Debenedetti, Pablo G.; Raghavan, V.; Borick, Steven S.

doi:10.1021/j100164a066

Cited by 116 publications

(117 citation statements)

References 9 publications

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“…The importance of this task argues for a strong effort in implementing MD programs for waterlike potentials on new powerful parallel computers. Analytical work on simple potentials showing a density maximum should also be pursued; already such approaches have revealed a rich set of possible behaviors [16][17][18][19][20][34][35][36][37] ]. If our data are confirmed by these extensive checks, then it will become important to perform experiments as close as possible to the new critical point, which according to the P and T shift used above, should be located in real water at T = 185 K and P = 120 Pa. At the same time, we hope that measurements in the stretched region can be extended to search for the change in slope of the line of density maxima [38 ].…”

Section: A New Critical Point?mentioning

confidence: 99%

“…Further important progress in this field has been made by Speedy [9] for the case of water and generalized to arbitrary fluids by Debenedetti and his colleagues [16][17][18][19][20]. They have observed that liquids having a line of density maxima which has a negative slope in the P-T plane of their phase diagram should possess a region where the line of density maxima and the liquid spinodal line meet.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Is there a second critical point in liquid water?

Stanley

Angell

Essmann

et al. 1994

Physica A: Statistical Mechanics and its Applications

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The supercooled and stretched regions of the phase diagram of simulated liquid water are investigated by calculating the equation of state of the ST2 and TIP4P pair-potentials. We find that simulated water does not display a re-entrant spinodal and that the projection of the density maximum line in the plane of pressure and temperature becomes positively sloped on stretching. The well-known anomalous behavior of supercooled water is tentatively associated with the existence of an inaccessible critical point. Evidence is presented that suggests the association of this new critical point with the transition between low density and high density amorphous solid water. We show how the observed transformation behavior of the two forms of amorphous solid water can be explained in terms of a first order phase transition, via a consideration of the limits of metastability associated with this kind of transition, and support this interpretation with simulations of the amorphous solid. We therefore propose a phase diagram which accounts for the behavior of both liquid and amorphous solid water.

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Section: A New Critical Point?mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Is there a second critical point in liquid water?

Stanley

Angell

Essmann

et al. 1994

Physica A: Statistical Mechanics and its Applications

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“…Simple spherically-symmetric potentials with a 'core-softened' or a repulsive interaction at short distances are able to generate water-like density and diffusion anomalies [6,7,8,9,10,11,12,13], and can even show a liquid-liquid transition [12]. These findings in simple liquids imply that strong orientational interactions (as observed in water or silica) are not a necessary condition for a liquid to have thermodynamic and dynamical anomalies.…”

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confidence: 99%

Structural Order for One-Scale and Two-Scale Potentials

et al. 2005

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We perform molecular dynamics simulations to investigate the relationship between structural order and water-like dynamic and thermodynamic anomalies in spherically-symmetric potentials having either one or two characteristic length scales. Structural order is characterized by translational and orientational order parameters. We find that (i) dynamic and thermodynamic anomalies exist for both one-scale and two-scale ramp potentials, and (ii) water-like structural order anomalies exist only for the two-scale ramp potential. Our findings suggest that the water-like relationship between structural order and anomalies is related to the presence of two different length scales in the potential.

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“…1 was chosen to mimic the three length scales and energies scales employed in the one dimensional case. The three length scales are identified by the change of the slope in the force 4 . The accessibility of the three length scales and the presence of the density anomalous region in the stable region of the pressure-temperature phase diagram is obtained by making the forces smooth and positive 28 .…”

mentioning

confidence: 99%

Multiple liquid-liquid critical points and density anomaly in core-softened potentials

2013

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The relation between liquid-liquid phase transitions and waterlike density anomalies in coresoftened potentials of fluids was investigated in an exactly solvable one dimensional lattice model and a in a three dimensional fluid with fermi-like potential, the latter by molecular dynamics. Both systems were shown to present three liquid phases, two liquid-liquid phase transitions closely connected to two distinct regions of anomalous density increase. We propose that an oscillatory behavior observed on the thermal expansion coefficient as a function of pressure can be used as a signature of the connection between liquid-liquid phase and density.PACS numbers: 61.20. Gy, The phase behavior of single component systems as particles interacting via the o-called core-softened (CS) potentials has received attention since the pioneering work of Stell and Hemmer proposing the possibility of a second critical point in addition to the usual liquidgas critical point 1 . These potentials exhibit a repulsive core with a softening region with a shoulder or a ramp 1-3 which are analytically and computationally tractable while being capable of retaining the qualitative features of the real fluid systems. Furthermore, Debenedetti and collaborators 4 using thermodynamic arguments showed that the isobaric thermal expansion coefficient (α) of these potentials might have an anomalous negative value and consequently a region where density increases with temperature. Since for high temperatures density decreases with temperature these potentials can exhibit a temperature of maximum density (TMD) connecting the two regions.The thermodynamic anomalies predicted by these models occur in liquids such as Te 5 , Ga, Bi 6 , S 7,8 , liquid water 9 , and Ge 15 Te 85 10 , and were found in simulations for silica 11,12 , silicon 13 , and BeF 2 11 . In addition experiments in phosphorous indicate the presence of a liquidliquid phase transition 14 and similar transitions were observed by simulations in models of silica 15 , silicon 13 and liquid water 16 .In the particular case of water the hypothesis of the existence of two liquid phases has been indirectly supported by experimental results in confined systems 17 . In spite of the limit of 235 K below which water cannot be found in the liquid phase without crystallization, two amorphous phases, a low density amorphous phase and a high density amorphous phase, were observed at much lower temperatures and their relation to a metastable liquidliquid phase transition was argued 18 . More recently a third amorphous phase, the very high density amorphous phase, has been observed 19 what suggests the possibility of the existence of the very high density liquid phase.Therefore the issue of a liquid-liquid phase transition and its connection with the existence of a region in the pressure-temperature phase diagram where the density decreases with the decrease of temperature is itself an interesting topic. It is accepted that the presence of two accessible length scales in the potential allow for the system to ...

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Spinodal curve of some supercooled liquids

Cited by 116 publications

References 9 publications

Is there a second critical point in liquid water?

Is there a second critical point in liquid water?

Structural Order for One-Scale and Two-Scale Potentials

Multiple liquid-liquid critical points and density anomaly in core-softened potentials

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