Communication: Minimum in the thermal conductivity of supercooled water: A computer simulation study

Bresme, Fernando; Biddle, John; Sengers, J. V.; Анисимов, М. А.

doi:10.1063/1.4873167

Cited by 20 publications

(28 citation statements)

References 38 publications

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“…We estimate that this is near liquid-liquid coexistence based on the equation of state data reported by Paschek [16], which predicts that TIP5P's liquid-liquid critical point is located at 210 K and 3.1 kbar. Literature estimates of the liquid-liquid critical temperature and pressure for TIP4P/2005 [17,18,19,20] vary between 193 and 182 K and 1.7 and 1.4 kbar, respectively. As a result, simulations for TIP4P/2005 were performed at 185 K and 1.8 kbar.…”

Section: Resultsmentioning

confidence: 99%

Density and bond-orientational relaxations in supercooled water

et al. 2016

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Recent computational studies have reported evidence of a metastable liquid-liquid phase transition (LLPT) in molecular models of water under deeply supercooled conditions. A competing hypothesis suggests, however, that non-equilibrium artifacts associated with coarsening of the stable crystal phase have been mistaken for an LLPT in these models. Such artifacts are posited to arise due to a separation of time scales in which density fluctuations in the supercooled liquid relax orders of magnitude faster than those associated with bond-orientational order. Here, we use molecular simulation to investigate the relaxation of density and bondorientational fluctuations in three molecular models of water (ST2, TIP5P and TIP4P/2005) in the vicinity of their reported LLPT. For each model, we find that density is the slowly relaxing variable under such conditions. We also observe similar behavior in the coarse-grained mW model of water. Our findings therefore challenge the key physical assumption underlying the competing hypothesis.

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Section: Resultsmentioning

confidence: 99%

Density and bond-orientational relaxations in supercooled water

et al. 2016

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“…Symbols indicate the simulated values: squares (with error bars) obtained by Bresme et al 257 and circles (without error bars) obtained previously by Abascal and Vega. 27 Curves represent values calculated from the two-structure equation of state.…”

Section: Nucleation Of Ice From Supercooled Watermentioning

confidence: 97%

Section: Nucleation Of Ice From Supercooled Watermentioning

confidence: 99%

Water: A Tale of Two Liquids

et al. 2016

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Water is the most abundant liquid on earth and also the substance with the largest number of anomalies in its properties. It is a prerequisite for life and as such a most important subject of current research in chemical physics and physical chemistry. In spite of its simplicity as a liquid, it has an enormously rich phase diagram where different types of ices, amorphous phases, and anomalies disclose a path that points to unique thermodynamics of its supercooled liquid state that still hides many unraveled secrets. In this review we describe the behavior of water in the regime from ambient conditions to the deeply supercooled region. The review describes simulations and experiments on this anomalous liquid. Several scenarios have been proposed to explain the anomalous properties that become strongly enhanced in the supercooled region. Among those, the second critical-point scenario has been investigated extensively, and at present most experimental evidence point to this scenario. Starting from very low temperatures, a coexistence line between a high-density amorphous phase and a low-density amorphous phase would continue in a coexistence line between a high-density and a low-density liquid phase terminating in a liquid–liquid critical point, LLCP. On approaching this LLCP from the one-phase region, a crossover in thermodynamics and dynamics can be found. This is discussed based on a picture of a temperature-dependent balance between a high-density liquid and a low-density liquid favored by, respectively, entropy and enthalpy, leading to a consistent picture of the thermodynamics of bulk water. Ice nucleation is also discussed, since this is what severely impedes experimental investigation of the vicinity of the proposed LLCP. Experimental investigation of stretched water, i.e., water at negative pressure, gives access to a different regime of the complex water diagram. Different ways to inhibit crystallization through confinement and aqueous solutions are discussed through results from experiments and simulations using the most sophisticated and advanced techniques. These findings represent tiles of a global picture that still needs to be completed. Some of the possible experimental lines of research that are essential to complete this picture are explored.

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“…it is difficult to think how empirical potentials can contribute to problems where water is involved in chemical reactions, or when computing electronic spectra. At the same time, it is difficult that approaches A or B can attack problems involving hundred of thousand of water molecules or very long times (for instance, nucleation and supercooled water [80][81][82] or the conformational changes in proteins). Our point of view is that the four approaches are complementary.…”

Section: Nmentioning

confidence: 99%

Water: one molecule, two surfaces, one mistake

Vega

2015

Molecular Physics

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In order to rigorously evaluate the energy and dipole moment of a certain configuration of molecules one needs to solve the Schrödinger equation. Repeating this for many different configurations allows one to determine the potential energy surface (PES) and the dipole moment surface (DMS). Since the early days of computer simulation it has been implicitly accepted that for empirical potentials the charges used to fit the PES should also be used to describe the DMS. This is a mistake. Partial charges are not observable magnitudes. They should be regarded as adjustable fitting parameters. Optimal values used to describe the PES are not necessarily the best to describe the DMS. One could use two fits: one for the PES, and another for the DMS. This is a common practice in the quantum chemistry community, but not used so often by the community performing computer simulations. This idea affects all types of modelling of water (with the exception of ab-initio calculations) from coarse grained to non-polarizable and polarizable models.We anticipate that an area that will benefit dramatically from having both, a good PES and a good DMS, is the modelling of water in the presence of electric fields.

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Communication: Minimum in the thermal conductivity of supercooled water: A computer simulation study

Cited by 20 publications

References 38 publications

Density and bond-orientational relaxations in supercooled water

Density and bond-orientational relaxations in supercooled water

Water: A Tale of Two Liquids

Water: one molecule, two surfaces, one mistake

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