Pattern of property extrema in supercooled and stretched water models and a new correlation for predicting the stability limit of the liquid state

Uralcan, Betül; Latinwo, Folarin; Debenedetti, Pablo G.; Анисимов, М. А.

doi:10.1063/1.5078446

Cited by 11 publications

(6 citation statements)

References 66 publications

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“…In addition, the LLCP scenario provides a natural framework to understand the anomalous behavior of binary aqueous solutions [23]. We also note that the LLCP scenario is strongly supported by computer simulations of many classical water models where a LLCP is found at low temperatures [9,[24][25][26][27][28][29][30].…”

Section: Introductionsupporting

confidence: 53%

Nuclear quantum effects on the thermodynamic response functions of a polymorphic waterlike monatomic liquid

Liu

Sun

Eltareb

et al. 2020

Phys. Rev. Research

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Water and hydrogen are examples of substances proposed to exhibit a liquid-liquid critical point (LLCP) at conditions where nuclear quantum effects are relevant. The LLCP is usually accompanied by lines of maxima in density ρ and thermodynamic response functions, such as isothermal compressibility κ T and isobaric heat capacity C P , in the supercritical region of the P-T plane. In the case of water, the ρand κ T-maxima lines can be accessed in experiments, while, instead, the LLCP has not been observed due to rapid crystallization. In this work, we study the nuclear quantum effects on a monatomic liquid that exhibits waterlike anomalous properties and a LLCP. By performing path-integral Monte Carlo simulations with different values of the Planck's constant h, we are able to explore how the location of the LLCP in the P-T plane and, in particular, the maxima lines in the supercritical region, shift as the system evolves from classical, h = 0, to quantum, h > 0. We find that as the quantum nature of the liquid (as quantified by h) increases and the atoms in the liquid become more delocalized, the LLCP shifts towards higher pressures and lower temperatures while the LLCP volume remains constant. Similar shifts (towards higher pressures and lower temperatures) are found in the case of the C P-and κ T-maxima lines. Instead, the ρ-maxima line extends towards higher temperatures and expands over a wider pressure interval as the liquid becomes more quantum. It follows that the nuclear quantum effects on the location of the LLCP may be estimated from the shift in C P-and κ T-maxima lines but not on measurements of the ρ-maxima line. Interestingly, nuclear quantum effects considerably alter the slope of the liquid-liquid coexistence line and C P-maxima line in the P-T plane while the slope of the κ T-maxima line along the Widom line is barely affected. We discuss briefly the implications of our results to the case of H 2 O/D 2 O.

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Section: Introductionsupporting

confidence: 53%

Nuclear quantum effects on the thermodynamic response functions of a polymorphic waterlike monatomic liquid

Liu

Sun

Eltareb

et al. 2020

Phys. Rev. Research

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“…This follows from the expectation that the T md will drop below the freezing point with increasing pressure. 52 …”

Section: Resultsmentioning

confidence: 99%

“…It is interesting to note that while the experiments do not exhibit a temperature of maximum density ( T md ) at this elevated pressure, the simulations predict a T md in the supercooled regime at −0.4 ± 0.2 °C. This follows from the expectation that the T md will drop below the freezing point with increasing pressure …”

Section: Resultsmentioning

confidence: 99%

Bridging Gaussian Density Fluctuations from Microscopic to Macroscopic Volumes: Applications to Non-Polar Solute Hydration Thermodynamics

2021

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The hydration of hydrophobic solutes is intimately related to the spontaneous formation of cavities in water through ambient density fluctuations. Information theory-based modeling and simulations have shown that water density fluctuations in small volumes are approximately Gaussian. For limiting cases of microscopic and macroscopic volumes, water density fluctuations are known exactly and are rigorously related to the density and isothermal compressibility of water. Here, we develop a theory—interpolated gaussian fluctuation theory (IGFT)—that builds an analytical bridge to describe water density fluctuations from microscopic to molecular scales. This theory requires no detailed information about the water structure beyond the effective size of a water molecule and quantities that are readily obtained from water’s equation-of-state—namely, the density and compressibility. Using simulations, we show that IGFT provides a good description of density fluctuations near the mean, that is, it characterizes the variance of occupancy fluctuations over all solute sizes. Moreover, when combined with the information theory, IGFT reproduces the well-known signatures of hydrophobic hydration, such as entropy convergence and solubility minima, for atomic-scale solutes smaller than the crossover length scale beyond which the Gaussian assumption breaks down. We further show that near hydrophobic and hydrophilic self-assembled monolayer surfaces in contact with water, the normalized solvent density fluctuations within observation volumes depend similarly on size as observed in the bulk, suggesting the feasibility of a modified version of IGFT for interfacial systems. Our work highlights the utility of a density fluctuation-based approach toward understanding and quantifying the solvation of non-polar solutes in water and the forces that drive them toward surfaces with different hydrophobicities.

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“…Clear evidence of an LLPT has been reported [33] only for the ST2 model [34], for which finite-size scaling [35] confirms the existence of an LLCP. Only a weak divergence could be observed for other models such as the extended simple point charge (SPC/E) [36] or the TIP4P potential [37], while the possibility of an ADP for the TIP5P potential [38] is supported by recent simulation studies [39]. For the mW model [40] it has been shown [41] that the non-ideality in mixing two alternative local orders is entropy-driven, and that this is too weak to produce an LLPT.…”

Section: Introductionmentioning

confidence: 99%

Thermodynamic metric geometry of the two-state ST2 model for supercooled water

Mausbach

May

Ruppeiner

2019

The Journal of Chemical Physics

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Liquid water has anomalous liquid properties, such as its density maximum at 4 • C. An attempt at theoretical explanation proposes a liquid-liquid phase transition line in the supercooled liquid state, with coexisting low-density (LDL) and high-density (HDL) liquid states. This line terminates at a critical point. It is assumed that the LDL state possesses mesoscopic tetrahedral structures that give it solidlike properties, while the HDL is a regular random liquid. But the short-lived nature of these solid-like structures make them difficult to detect directly. We take a thermodynamic approach instead, and calculate the thermodynamic Ricci curvature scalar R in the metastable liquid regime. It is believed that solid-like structures signal their presence thermodynamically by a positive sign for R, with a negative sign typically present in less organized fluid states. Using thermodynamic data from ST2 computer simulations fit to a mean field (MF) two state equation of state, we find significant regimes of positive R in the LDL state, supporting the proposal of solid-like structures in liquid water. In addition, we review the theory, compute critical exponents, demonstrate the large reach of the MF critical regime, and calculate the Widom line using R. point, two-state equation of state, ST2 models, solid-like liquid water, critical type fluctuation, Widom line, correlation length.

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Pattern of property extrema in supercooled and stretched water models and a new correlation for predicting the stability limit of the liquid state

Cited by 11 publications

References 66 publications

Nuclear quantum effects on the thermodynamic response functions of a polymorphic waterlike monatomic liquid

Nuclear quantum effects on the thermodynamic response functions of a polymorphic waterlike monatomic liquid

Bridging Gaussian Density Fluctuations from Microscopic to Macroscopic Volumes: Applications to Non-Polar Solute Hydration Thermodynamics

Thermodynamic metric geometry of the two-state ST2 model for supercooled water

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