Glass polymorphism and liquid–liquid phase transition in aqueous solutions: experiments and computer simulations

Bachler, Johannes; Handle, Philip H.; Giovambattista, Nicolás; Loerting, Thomas

doi:10.1039/c9cp02953b

Cited by 38 publications

(45 citation statements)

References 310 publications

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“…Finally, our results allow for direct comparison with molecular dynamic simulations employing full-atomistic water models. This was not possible so far because LDA in experiments is usually prepared starting from ice I h , while in simulations, "LDA" (in fact, HGW) is prepared through ultrarapid cooling of liquid water (2). By contrast to experiments, vitrification is realized easily in simulations because it is rare to observe unseeded crystallization of water.…”

Section: Compatibility With Water Modelsmentioning

confidence: 99%

“…polyamorphism | glassy water | high-density amorphous ice | pressureinduced amorphization Two Liquids or a Mixture of Nanocrystals Poole et al (1) put forward the idea that the one-component system water could in fact be composed of two distinct liquids with differing densities (liquid polymorphism). Aimed at explaining the anomalous behavior of supercooled water, this model has remained in scientific debate for three decades (2)(3)(4)(5)(6)(7)(8). However, attempts to demonstrate the concept experimentally have not been conclusive because water readily crystallizes to ice in the temperature region where the two liquids could be separable.…”

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confidence: 99%

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Experimental evidence for glass polymorphism in vitrified water droplets

Bachler

Giebelmann

Loerting

2021

Proc. Natl. Acad. Sci. U.S.A.

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The nature of amorphous ices has been debated for more than 35 years. In essence, the question is whether they are related to ice polymorphs or to liquids. The fact that amorphous ices are traditionally prepared from crystalline ice via pressure-induced amorphization has made a clear distinction tricky. In this work, we vitrify liquid droplets through cooling at ≥106 K ⋅ s−1 and pressurize the glassy deposit. We observe a first order–like densification upon pressurization and recover a high-density glass. The two glasses resemble low- and high-density amorphous ice in terms of both structure and thermal properties. Vitrified water shows all features that have been reported for amorphous ices made from crystalline ice. The only difference is that the hyperquenched and pressurized deposit shows slightly different crystallization kinetics to ice I upon heating at ambient pressure. This implies a thermodynamically continuous connection of amorphous ices with liquids, not crystals.

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Section: Compatibility With Water Modelsmentioning

confidence: 99%

mentioning

confidence: 99%

Experimental evidence for glass polymorphism in vitrified water droplets

Bachler

Giebelmann

Loerting

2021

Proc. Natl. Acad. Sci. U.S.A.

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“…In this regard, it is important to keep in mind that only the LLCP scenario can satisfactorily explain the sharpness of such a glass-glass first-order-like phase transition [22]. 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: Introductionmentioning

confidence: 70%

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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“…We referred to Tm as the liquidus, and to Tm' as the onset of freezing, noting also that the latter event can be additionally affected by "interface ice" effects and the combination of "cold recrystallization/ice dissolution as discussed in the litterature. 34,35 In the intermediate region (45% < G < 70%), both situations (ice formation or not) occur depending on the thermal treatment, allowing the independent determination of Tg and Tg'. This is illustrated by our measurement for WG = 60% in Figure S3.…”

Section: Toc Graphicmentioning

confidence: 99%

“…The behaviors obtained in the porous matrixes were qualitatively similar to those of the bulk solutions, and are summarized in Figure 1 by a 3D plot of all the thermograms acquired on warming. [33][34][35][36][37] This similarity is due to the tendency of ice to crystallize in mesopores, which is no more the case in micropores (i.e. Rp = 1.0 nm).…”

Section: Toc Graphicmentioning

confidence: 99%

Extension and Limits of Cryoscopy for Nanoconfined Solutions

Malfait

Pouessel

Jani

et al. 2020

J. Phys. Chem. Lett.

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HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

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Glass polymorphism and liquid–liquid phase transition in aqueous solutions: experiments and computer simulations

Abstract: Water is an intriguing substance. It shows sharp and reversible transitions between amorphous ices and, possibly, a liquid–liquid phase transition. Here, we discuss how this behavior is altered by the addition of solutes, such as salts and alcohols.

Cited by 38 publications

References 310 publications

Experimental evidence for glass polymorphism in vitrified water droplets

Experimental evidence for glass polymorphism in vitrified water droplets

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

Extension and Limits of Cryoscopy for Nanoconfined Solutions

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