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Abstract Growth of ice crystals is ubiquitous around us, but we still do not know what is occurring at the forefront of crystallization. In general, the interfacial structure is inseparably involved in the microscopic ordering during crystal growth. However, despite its importance in nature and technology, the intrinsic role of the interfacial structure in the melt growth of ice remains to be elucidated. Here, using extensive molecular dynamics simulations, we comprehensively explore how supercooled water molecules are incorporated into the ice basal face. Structural and dynamic characterizations of the ice-water interface demonstrate that the ice basal face is sharp at the molecular level and its growth proceeds layer-by-layer through two-dimensional nucleation without any intermediate structures. We further quantify the crossover from layerwise to adhesive growth, called kinetic roughening, with the height difference correlation and the normal growth rate analysis. Moreover, we identify the presence of an ultra-low density water layer in contact with the structural interface, which assists two-dimensional nucleation at a small amount of supercooling without involving any triggers, such as dislocations.

The surfaces of ice crystals near the melting point are covered with thin liquid water layers, called quasi-liquid layers (QLLs), which play crucial roles in various chemical reactions in nature. So far, there have been many spectroscopic studies of such chemical reactions on ice surfaces, however, revealing the effects of atmospheric gases on ice surfaces remains an experimental challenge. In this study, we chose HNO3 as a model atmospheric gas, and directly observed the ice basal faces by advanced optical microscopy under partial pressure of HNO3 (~10−4 Pa), relevant to those found in the atmosphere. We found that droplets (HNO3-QLLs) appeared on ice surfaces at temperatures ranging from −0.9 to −0.2 °C with an increase in temperature, and that they disappeared at temperatures ranging from −0.6 to −1.3 °C with decreasing temperature. We also found that the size of the HNO3-QLLs decreased immediately after we started reducing the temperature. From the changes in size and the liquid−solid phase diagram of the HNO3-H2O binary system, we concluded that the HNO3-QLLs did not consist of pure water, but rather aqueous HNO3 solutions, and that the temperature and HNO3 concentration of the HNO3-QLLs also coincided with those along a liquidus line.

We review our recent study on step-bunching instability (SBI) of ice melt growth, one of the interfacial instabilities driven by self-organization of elementary step flow associated with crystal growth dynamics. With the aid of an advanced optical microscope and its combination with a two-beam interferometer, we realized quantitative in situ observations of the spatiotemporal dynamics of the SBI. This enables us to examine the origin of the SBI at the level of the step-step interaction. Our finding offers a significant clue to understanding the general mechanism of melt growth beyond ice-crystal growth, inseparably involving several broad research fields, including cryobiological, geophysical, and material branches. [ABSTRACT FROM AUTHOR]

Liquid-liquid transition (LLT) is the transformation of one liquid to another via first-order phase transition. For example, LLT in a molecular liquid, triphenyl phosphite, is macroscopically the transformation from liquid I in a supercooled state to liquid II in a glassy state. Reflecting the transformation from the liquid to glassy state, the LLT is accompanied by considerable slowing down of overall molecular dynamics, but little is known about how this proceeds at a molecular level coupled with the evolution of the order parameter. We report such information by performing time-resolved simultaneous measurements of dielectric spectroscopy and phase contrast microscopy/Raman spectroscopy by using a dielectric cell with transparent electrodes. We find that the temporal change in molecular mobility crucially depends on whether LLT is nucleation growth type occurring in the metastable state or SD type occurring in the unstable state. Furthermore, our results suggest that the molecular mobility is controlled by the local order parameter: more specifically, the local activation energy of molecular rotation is controlled by the local fraction of locally favored structures formed in the liquid. Our study sheds light on the temporal change in the molecular dynamics during LLT and its link to the order parameter evolution. [ABSTRACT FROM AUTHOR]

We measured the velocity Vstep of isolated elementary spiral steps and the distance Leq between adjacent equivalent spiral steps on ice basal faces by advanced optical microscopy. We determined the step kinetic coefficient β from Vstep measured under various supersaturations. We performed similar experiments under various temperatures T, and determined the temperature dependence of β of ice basal faces, for the first time, in the temperature range of −26.0 to −2.7 °C. When −6.2 ≤ T ≤ −2.7 °C, the value of β decreased significantly with decreasing T. In contrast, when −15.0 ≤ T ≤ −6.2 °C, the value of β increased with decreasing T, and had the maximum at T ≈ −15 °C. When −26.0 ≤ T ≤ −15.0 °C, the value of β decreased monotonically with decreasing T. Such complicated temperature dependence of β strongly implies the existence of unknown phenomena in the temperature range examined. To obtain a clue to the complicated behavior of β, we also measured dependence of Leq on surface supersaturation Δμsurf. When −13.0 ≤ T ≤ −3.2 °C, plots of Leq vs 1/Δμsurf satisfactorily follow the spiral growth model. However, when −26.0 ≤ T ≤ −15.0 °C, the Leq vs 1/Δμsurf plots do not follow any model: this temperature range agrees with the temperature range in which β decreased monotonically with decreasing T. [ABSTRACT FROM AUTHOR]

Since the pioneering prediction of surface melting by Michael Faraday, it has been widely accepted that thin water layers, called quasi-liquid layers (QLLs), homogeneously and completely wet ice surfaces. Contrary to this conventional wisdom, here we both theoretically and experimentally demonstrate that QLLs have more than two wetting states and that there is a first-order wetting transition between them. Furthermore, we find that QLLs are born not only under supersaturated conditions, as recently reported, but also at undersaturation, but QLLs are absent at equilibrium. This means that QLLs are a metastable transient state formed through vapor growth and sublimation of ice, casting a serious doubt on the conventional understanding presupposing the spontaneous formation of QLLs in ice-vapor equilibrium. We propose a simple but general physical model that consistently explains these aspects of surface melting and QLLs. Our model shows that a unique interfacial potential solely controls both the wetting and thermodynamic behavior of QLLs. [ABSTRACT FROM AUTHOR]

We have experimentally determined the surface tension-to-shear viscosity ratio (the so-called characteristic velocity) of quasiliquid layers (QLLs) on ice crystal surfaces from their wetting dynamics. Using an advanced optical microscope, whose resolution reaches the molecular level in the height direction, we directly observed the coalescent process of QLLs and followed the relaxation modes of their contact lines. The relaxation dynamics is known to be governed by the characteristic velocity, which allows us to access the physical properties of QLLs in a noninvasive way. Here we quantitatively demonstrate that QLLs, when completely wetting ices, have a thickness of 9 ± 3 nm and an approximately 200 times lower characteristic velocity than bulk water, whereas QLLs, when partially wetting ices, have a velocity that is 20 times lower than the bulk. This indicates that ice crystal surfaces significantly affect the physical properties of QLLs localized near the surfaces at a nanometer scale. [ABSTRACT FROM AUTHOR]

A liquid-liquid transition (LLT) in a single-component substance is an unconventional phase transition from one liquid to another. LLT has recently attracted considerable attention because of its fundamental importance in our understanding of the liquid state. To access the order parameter governing LLT from a microscopic viewpoint, here we follow the structural evolution during the LLT of an organic molecular liquid, triphenyl phosphite (TPP), by timeresolved small- and wide-angle X-ray scattering measurements. We find that locally favored clusters, whose characteristic size is a few nanometers, are spontaneously formed and their number density monotonically increases during LLT. This strongly suggests that the order parameter of LLT is the number density of locally favored structures and of nonconserved nature. We also show that the locally favored structures are distinct from the crystal structure and these two types of orderings compete with each other. Thus, our study not only experimentally identifies the structural order parameter governing LLT, but also may settle a longstanding debate on the nature of the transition in TPP, i.e., whether the transition is LLT or merely microcrystal formation. [ABSTRACT FROM AUTHOR]

Colloidal clusters are an unusual state of matter where tunable interactions enable a sufficient reduction in their degrees of freedom that their energy landscapes can become tractable - they form a playground for statistical mechanics and promise unprecedented control of structure on the submicron lengthscale. We study colloidal clusters in a system where a short-ranged polymer-induced attraction drives clustering, while a weak, long-ranged electrostatic repulsion prevents extensive aggregation. We compare experimental yields of cluster structures with theory which assumes simple addition of competing isotropic interactions between the colloids. Here we show that for clusters of size 4⩽m ⩽7, the yield of minimum energy clusters is much less than expected. We attribute this to an anisotropic self-organized surface charge distribution which leads to unexpected kinetic trapping. We introduce a model for the coupling between counterions and binding sites on the colloid surface with which we interpret our findings. [ABSTRACT FROM AUTHOR]

A microscopic understanding of crystal-melt interfaces, inseparably involved in the dynamics of crystallization, is a long-standing challenge in condensed matter physics. Here, using an advanced optical microscopy, we directly visualize growing interfaces between ice basal faces and quasiliquid layers (QLLs) during ice crystal growth. This system serves as a model for studying the molecular incorporation process of the crystal growth from a supercooled melt (the so-called melt growth), often hidden by inevitable latent heat diffusion and/or the extremely high crystal growth rate. We reveal that the growth of basal faces inside QLLs proceeds layer by layer via two-dimensional nucleation of monomolecular islands. We also find that the lateral growth rate of the islands is well described by the Wilson-Frenkel law, taking into account the slowing down of the dynamics of water molecules interfaced with ice. These results clearly indicate that, after averaging surface molecular fluctuations, the layer by layer stacking still survives even at the topmost layer on basal faces, which supports the kink-step-terrace picture even for the melt growth. [ABSTRACT FROM AUTHOR]