The anomalously high melting temperature of bilayer ice

Kastelowitz, Noah; Johnston, Jessica C.; Molinero, Valeria

doi:10.1063/1.3368793

Cited by 91 publications

(122 citation statements)

References 36 publications

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“…Here, the two outer layers are flat while the middle layer is puckered. The third and the fourth TL ices, found by Kastelowitz et al, 44 are planar (for D = 1.1−1.15 nm) and puckered (for D = 1.2−1.4 nm), respectively. In the planar TL ice, every water molecule has four HB nearestneighbors.…”

Section: Trilayer Icesmentioning

confidence: 94%

Highly Confined Water: Two-Dimensional Ice, Amorphous Ice, and Clathrate Hydrates

et al. 2014

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Understanding phase behavior of highly confined water, ice, amorphous ice, and clathrate hydrates (or gas hydrates), not only enriches our view of phase transitions and structures of quasi-two-dimensional (Q2D) solids not seen in the bulk phases but also has important implications for diverse phenomena at the intersection between physical chemistry, cell biology, chemical engineering, and nanoscience. Relevant examples include, among others, boundary lubrication in nanofluidic and lab-on-a-chip devices, synthesis of antifreeze proteins for ice-growth inhibition, rapid cooling of biological suspensions or quenching emulsified water under high pressure, and storage of H2 and CO2 in gas hydrates. Classical molecular simulation (MD) is an indispensable tool to explore states and properties of highly confined water and ice. It also has the advantage of precisely monitoring the time and spatial domains in the sub-picosecond and sub-nanometer scales, which are difficult to control in laboratory experiments, and yet allows relatively long simulation at the 10(2) ns time scale that is impractical with ab initio molecular dynamics simulations. In this Account, we present an overview of our MD simulation studies of the structures and phase behaviors of highly confined water, ice, amorphous ice, and clathrate, in slit graphene nanopores. We survey six crystalline phases of monolayer (ML) ice revealed from MD simulations, including one low-density, one mid-density, and four high-density ML ices. We show additional supporting evidence on the structural stabilities of the four high-density ML ices in the vacuum (without the graphene confinement), for the first time, through quantum density-functional theory optimization of their free-standing structures at zero temperature. In addition, we summarize various low-density, high-density, and very-high-density Q2D bilayer (BL) ice and amorphous ice structures revealed from MD simulations. These simulations reinforce the notion that the nanoscale confinement not only can disrupt the hydrogen bonding network in bulk water but also can allow satisfaction of the ice rule for low-density and high-density Q2D crystalline structures. Highly confined water can serve as a generic model system for understanding a variety of Q2D materials science phenomena, for example, liquid-solid, solid-solid, solid-amorphous, and amorphous-amorphous transitions in real time, as well as the Ostwald staging during these transitions. Our simulations also bring new molecular insights into the formation of gas hydrate from a gas and water mixture at low temperature.

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Section: Trilayer Icesmentioning

confidence: 94%

Highly Confined Water: Two-Dimensional Ice, Amorphous Ice, and Clathrate Hydrates

et al. 2014

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“…42 Molecular simulations with the mW model are more than two orders of magnitude computationally more efficient than with atomistic water models using Ewald sums. [42][43][44][45][46][47] In previous work we used largescale molecular dynamics ͑MD͒ simulations with the mW model to characterize the evolution of the structure of liquid water from stable liquid at 350 K to the LDA glass at 100 K, when the liquid is cooled at the slowest rate that avoids ice crystallization. The coarse grained model reproduces the structure of liquid water, the LDA glass, ice and clathrate hydrates, and the thermodynamics of the phase transformations between them.…”

Section: Introductionmentioning

confidence: 99%

Ice crystallization in water’s “no-man’s land”

Moore

Molinero

2010

The Journal of Chemical Physics

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The crystallization of water at 180 K is studied through large-scale molecular dynamics simulations with the monatomic water model mW. This temperature is in the middle of water's "no-man's land," where rapid ice crystallization prevents the elucidation of the structure of liquid water and its transformation into ice with state of the art experimental methods. We find that critical ice nuclei (that contain less than ten water molecules) form in a time scale shorter than the time required for the relaxation of the liquid, suggesting that supercooled liquid water cannot be properly equilibrated in this region. We distinguish three stages in the crystallization of water at 180 K: concurrent nucleation and growth of ice, followed by consolidation that decreases the number density of ice nuclei, and finally, slow growth of the crystallites without change in their number density. The kinetics of the transformation along the three stages is well described by a single compacted exponential Avrami equation with n approximately 1.7. This work confirms the coexistence of ice and liquid after water is crystallized in "no-man's land": the formation of ice plateaus when there is still 15%-20% of liquid water in the systems, thinly dispersed between ice I crystals with linear dimensions ranging from 3 to 10 nm. We speculate that the nanoscopic size of the crystallites decreases their melting point and slows their evolution toward the thermodynamically most stable fully crystalline state.

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“…[5][6][7][8] The mW model has been extensively validated for the simulation of supercooled liquid water and ice, and for the study of the crystallization of bulk water, water confined in nanopores and water nanodroplets. [4][5][6][7][9][10][11][12][13][14][15][16][17][18] The crystallization of mW water was investigated through extensive large-scale molecular dynamics simulations using LAMMPS package. The rates of crystallization were determined from several hundred independent simulations analyzed with the mean first passage time method in the implementation of Ref.…”

Section: Model and Methodsmentioning

confidence: 99%

What determines the homogeneous freezing temperature of water?

Molinero

2013

AIP Conference Proceedings

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One of water's puzzles is what determines the lowest temperature at which liquid water and aqueous solutions can be cooled before freezing to ice. The increase of ice nucleation rates as water is supercooled correlates with a dramatic increase in the heat capacity and compressibility of supercooled water, raising the question of whether a structural transformation occurring within the liquid phase controls the rate of nucleation of ice. We used molecular simulations to elucidate the mechanism and compute the rates of water freezing and their relation to the thermodynamics and structure of supercooled water. A main finding of our study is that the kinetics of water freezing is controlled by a structural transformation in supercooled liquid water that steeply increases the fraction of four-coordinated water molecules in the liquid, blurring the boundary between the liquid and crystal states. The results of the molecular simulations and of calculations using classical nucleation theory with available experimental data, indicate that the crystallization rate of bulk water reaches a maximum at ~224 K, a few degrees below the experimental temperature of homogeneous nucleation of ice. We predict that below this temperature supercooled bulk liquid water crystallizes at a rate faster than it can equilibrate, therefore is beyond its limit of metastability. Our results provide a microscopic foundation to the known correlation between nonequilibrium freezing temperatures and the thermodynamics of supercooled liquid water. We will discuss the effect of confinement of water in nanopores and as nanodroplets on the mechanisms and temperatures of crystallization of ice as well as on the structure of the ice formed at temperature close to the limit of supercooling.

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The anomalously high melting temperature of bilayer ice

Cited by 91 publications

References 36 publications

Highly Confined Water: Two-Dimensional Ice, Amorphous Ice, and Clathrate Hydrates

Highly Confined Water: Two-Dimensional Ice, Amorphous Ice, and Clathrate Hydrates

Ice crystallization in water’s “no-man’s land”

What determines the homogeneous freezing temperature of water?

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