Effect of dissolved salt on the anomalies of water at negative pressure

Zaragoza, Alberto; Tripathi, Chandra Shekhar Pati; Gonzalez, Miguel A.; Abascal, J. L. F.; Caupin, Frédéric; Valeriani, Chantal

doi:10.1063/5.0002745

Cited by 5 publications

(5 citation statements)

References 49 publications

(58 reference statements)

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“…Molecular simulation has been recognized as a powerful tool to investigate the properties of molecular systems. It is complementary to experimental measurements and may be of great help in conditions under which performing an experiment is a challenging task. − However, to the best of our knowledge, it has never been used to investigate seawater. There are two likely reasons for that.…”

Section: Introductionmentioning

confidence: 99%

“In Silico” Seawater

Zerón

Gonzalez

Errani

et al. 2021

J. Chem. Theory Comput.

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Many important processes affecting the earth's climate are determined by the physical properties of seawater. In addition, desalination of seawater is a significant source of drinking water for the human population living in coastal areas. Since the physical properties of seawater governing these processes depend on the molecular interactions among its components, a deeper knowledge of seawater at the molecular level would contribute to a better understanding of these phenomena. However, in strong contrast with the situation in other areas such as biomolecules or materials science, molecular simulation studies reporting the physical properties of seawater are currently lacking. This is probably due to the usual perception of the seawater composition being too complex to approach. This point of view ignores the fact that physical properties of seawater are dependent on a single parameter representing the composition, namely the salinity. This is because the relative proportions of any two major constituents of seasalt are always the same. Another obstacle to performing molecular simulations of seawater could have been the unavailability of a satisfactory force field representing the interactions between water molecules and dissolved substances. However, this drawback has recently been overcome with the proposal of the Madrid-2019 force field. In this work we show for the first time that molecular simulation of seawater is feasible. We have performed molecular dynamics simulations of a system, the composition of which is close to the average composition of standard seawater and with the molecular interactions given by the Madrid-2019 force field. In this way we are able to provide quantitative or semiquantitative predictions for a number of relevant physical properties of seawater for temperatures and salinities from the oceanographic range to those relevant to desalination processes. The computed magnitudes include static (density), dynamical (viscosity and diffusion coefficients), structural (ionic hydration, ion−ion distribution functions), and interfacial (surface tension) properties.

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Section: Introductionmentioning

confidence: 99%

“In Silico” Seawater

Zerón

Gonzalez

Errani

et al. 2021

J. Chem. Theory Comput.

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“…In addition, we have also reported the κ T max along isochores ranging from low to high densities. A similar behavior of the κ T max lines in the P – T plane is reported in recent studies on TIP4P/2005 water. , Interestingly, we note that the κ T max -isochore line crosses the κ T max -isobar line in the P – T plane at the temperature of maximum κ T on isochoric cooling for the density where κ T max -isochore shows a minimum on compression/decompression (see Figure B). This result suggests that the peculiar shape of the LV spinodal is responsible for the distortion of the κ T max -isochore line at moderately high and negative pressures in the P – T plane.…”

Section: Phase Diagrammentioning

confidence: 99%

“…This ability to withstand strong negative pressure is attributed to the strong cohesive forces between the molecules in liquid water. Recent computational and experimental studies − further suggest rich anomalous thermodynamic behavior of liquid water at negative pressure conditions, including doubly metastable conditions where liquid water is simultaneously metastable with respect to both vapor and ice phases. The thermodynamic anomalies at negative pressures include the retracing behavior of the TMD line, the anomalous increase of the thermodynamic response functions (such as isothermal compressibility κ T and isobaric heat capacity C P ) on isobaric cooling, and the sound velocity minimum and isothermal compressibility maximum on isochoric cooling. − The anomalous increase of the thermodynamic response functions on isobaric cooling at ambient and negative pressures is often attributed to the existence of a hypothetical liquid–liquid transition (LLT) at high pressures and the associated Widom line. ,,− The anomalous temperature ( T ) dependence of the sound velocity and isothermal compressibility along isochores at negative pressures was attributed recently to the peculiar reentrant behavior of the liquid–vapor (LV) spinodal in the temperature-density ( T – ρ) plane …”

Section: Introductionmentioning

confidence: 99%

“…In contrast to the liquid water’s anomalous behavior which is well-studied at ambient as well as extreme conditions in both the computer simulation and experimental studies, − ,− relatively few studies have investigated the nucleation (vapor or ice) from metastable liquid water near ambient − and negative pressure conditions, ,,,,− and even fewer studies have explored the interplay between the observed (metastable) water’s thermodynamic anomalies and the nucleation barrier. ,,− In a recent seminal study, using computer simulations of TIP4P/Ice water, Vega and co-workers investigated ice nucleation from metastable liquid water at pressures ranging from high to negative pressures close to the LV spinodal. They reported an anomalous (nonmonotonic) dependence of the ice nucleation barrier on pressure along isotherms where the nucleation barrier reaches a minimum at negative pressures in the doubly metastable region of the phase plane.…”

Section: Introductionmentioning

confidence: 99%

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Anomalous Vapor and Ice Nucleation in Water at Negative Pressures: A Classical Density Functional Theory Study

2023

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In contrast to the abundance of work on the anomalous behavior of water, the relationship between the water’s thermodynamic anomalies and kinetics of phase transition from metastable water is relatively unexplored. In this work, we have employed classical density functional theory to provide a unified and coherent picture of nucleation (both vapor and ice) from metastable water at negative pressure conditions. Our results suggest a peculiar nonmonotonic temperature dependence of vapor–liquid surface tension at temperatures where vapor–liquid coexistence is metastable with respect to the ice phase. The vapor nucleation barrier on isochoric cooling also shows a nonmonotonic temperature dependence. We further report that, for low density isochores, the temperature of the minimum vapor nucleation barrier ( T Δ Ω v / min * ) does not coincide with the temperature of maximum density (TMD) where metastability is maximum. The difference between the T normalΔ normalΩ normalv / min * and the TMD, however, decreases with increasing the density of the isochore. The vapor nucleation barrier along isobars shows an interesting crossover behavior in the vicinity of the Widom line on lowering the temperature. Our results on the ice nucleation suggest an anomalous retracing behavior of the nucleation barrier along isotherms at negative pressures and theoretically validate the recent findings that the reentrant ice(Ih)-liquid coexistence line can induce a drastic change in the kinetics of ice nucleation. Thus, this study establishes a direct connection between the metastable water’s thermodynamic anomalies and the (vapor and ice) nucleation kinetics. In addition, this study provides deeper insights into the origin of the isothermal compressibility maximum on isochoric cooling.

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“…We recently started to apply the Brillouin method to salt solutions [71], in order to measure the effect of solutes on water's anomalies.…”

Section: The Equation Of State At Negative Pressurementioning

confidence: 99%