We propose the first Skyrmion Spin Ice, realized via confined, interacting liquid crystal skyrmions. Skyrmions in a chiral nematic liquid crystal behave as quasi-particles that can be dynamically confined, bound, and created or annihilated individually with ease and precision. We show that these quasi-particles can be employed to realize binary variables that interact to form ice-rule states. Because of their unique versatility, liquid crystal skyrmions can open entirely novel avenues in the field of frustrated systems. More broadly, our findings also demonstrate the viability of LC skyrmions as elementary degrees of freedom in the design of collective complex behaviors.
When chiral liquid crystals or magnets are subjected to applied fields or other anisotropic environments, the competition between favored twist and anisotropy leads to the formation of complex defect structures. In some cases, the defects are skyrmions, which have 180° double twist going outward from the center, and hence can pack together without singularities in the orientational order. In other cases, the defects are merons, which have 90° double twist going outward from the center; packing such merons requires singularities in the orientational order. In the liquid crystal context, a latti…
Cholesteric liquid crystals experience geometric frustration when they are confined between surfaces with anchoring conditions that are incompatible with the cholesteric twist. Because of this frustration, they develop complex topological defect structures, which may be helicoids or skyrmions. We develop a theory for these structures, which extends previous theoretical research by deriving exact solutions for helicoids with the assumption of constant azimuth, calculating numerical solutions for helicoids and skyrmions with varying azimuth, and interpreting the results in terms of competition b…
Recent experiments have found that applied electric fields can induce motion of skyrmions in chiral nematic liquid crystals. To understand the magnitude and direction of the induced motion, we develop a coarse-grained approach to describe dynamics of skyrmions, similar to our group's previous work on the dynamics of disclinations. In this approach, we represent a localized excitation in terms of a few macroscopic degrees of freedom, including the position of the excitation and the orientation of the background director. We then derive the Rayleigh dissipation function, and hence the equations …
Skyrmions have attracted rapidly growing interest due to their topological properties and unique aspects for potential novel applications such as data storage and soft robotics. They can also serve as key elements for materials by design, self-assembly, and functional soft materials. While not real particles, these skyrmions behave like particles-they interact with each other and can be actuated by means of electric field, surface anchoring, and light. On the other hand, they are field configurations which have properties not possessed by real particles. Here, we show that, by means of alignme…
We study axially symmetrical 3D skyrmionic particles (torons, hopfions) in a thin homeotropic cell filled with a cholesteric liquid crystal. In this case, the contribution of the chirality term on far distances becomes small and a 3D skyrmion can be described as a very specific particle in nematic with multipole moments of different chiralities. We show that small skyrmions asymptotically can be presented as a particle with six multipole moments. Thus, we find the exact analytical solution for the far field director configuration around the 3D skyrmion and the exact analytical expression for t…
Light provides a powerful means of controlling physical behavior of materials but is rarely used to power and guide active matter systems. We demonstrate optical control of liquid crystalline topological solitons dubbed "skyrmions", which recently emerged as highly reconfigurable inanimate active particles capable of exhibiting emergent collective behaviors like schooling. Because of a chiral nematic liquid crystal's natural tendency to twist and its facile response to electric fields and light, it serves as a testbed for dynamic control of skyrmions and other active particles. Using ambient-i…
We analyze the interaction with uniform external fields of nematic liquid crystals within a recent generalized free-energy posited by Virga and falling in the class of quartic functionals in the spatial gradients of the nematic director. We review some known interesting solutions, i. e., uniform heliconical structures, which correspond to the so-called twist-bend nematic phase and we also study the transition between this phase and the standard uniform nematic one. Moreover, we find liquid crystal configurations, which closely resemble some novel, experimentally detected, structures called Sky…
Within the framework of Oseen-Frank theory, we analyse the static configurations for chiral liquid crystals. In particular, we find numerical solutions for localised axisymmetric states in confined chiral liquid crystals with weak homeotropic anchoring at the boundaries. These solutions describe the distortions of two-dimensional skyrmions, known as either \textit{spherulites} or \textit{cholesteric bubbles}, which have been observed experimentally in these systems. Relations with nonlinear integrable equations have been outlined and are used to study asymptotic behaviors of the solutions. By …
The lack of accurate low-energy electron scattering cross sections for liquid water is a substantial source of uncertainty in the modelling of radiation chemistry and biology. The use of existing amorphous ice scattering cross sections for lack of liquid data has been discussed controversially over decades. Here, we compare experimental photoemission data of liquid water with corresponding predictions using amorphous ice cross sections, with the aim of resolving the debate regarding the difference of electron scattering in liquid water and amorphous ice. We find very similar scattering propert…
Chiral condensed matter systems, such as liquid crystals and magnets, exhibit a host of spatially localized topological structures that emerge from the medium's tendency to twist and its competition with confinement and field coupling effects. We show that the strength of perpendicular surface boundary conditions can be used to control the structure and topology of solitonic and other localized field configurations. By combining numerical modeling and three-dimensional imaging of the director field, we reveal structural stability diagrams and inter-transformation of twisted walls and fingers, …
Skyrmions are particle-like topological excitations, studied in various condensed matter systems and models of high-energy physics (HEP). They occur as stable spin textures in certain planar magnetic materials and as configurations in chiral nematic liquid crystals, having been originally proposed as model of atomic nuclei. Since magnetic Skyrmions can be accelerated with a current, they have the potential to encode bits in low-power magnetic storage devices. Drawing on techniques from HEP, we demonstrate that magnetic and liquid crystal Skyrmions interact like orientation dependent, localised…
The x-ray absorption spectra of water and ice are calculated with a many-body approach for electron-hole excitations. The experimental features, including the small effects of temperature change in the liquid, are quantitatively reproduced from molecular configurations generated by ab-initio molecular dynamics. The spectral difference between the solid and the liquid is due to two major short range order effects. One, due to breaking of hydrogen bonds, enhances the pre-edge intensity in the liquid. The other, due to a non-bonded molecular fraction in the first coordination shell, affects the m…
Topological solitons, such as skyrmions, arise in field theories of systems ranging from Bose-Einstein condensates to optics, particle physics, and cosmology, but they are rarely accessible experimentally. Chiral nematic liquid crystals provide a platform to study skyrmions because of their natural tendency to form twisted structures arising from the lack of mirror symmetry at the molecular level. However, large-scale dynamic control and technological utility of skyrmions remain limited. Combining experiments and numerical modeling of chiral liquid crystals with optically controlled helical pi…
When materials freeze, they often undergo damage due to ice growth. Although this damage is commonly ascribed to the volumetric expansion of water upon freezing, it is usually driven by suction of water towards growing ice crystals. The freezing of this additional water can cause a large build up of stress. Here, we study this process by producing a stable ice/water interface in a controlled temperature gradient, and measuring the deformation of the confining boundary. Analysis of the deformation field reveals stresses applied to the boundary with $\mathcal{O}(μ\mathrm{m})$ resolution. Globall…
We investigate the structural similarities between liquid water and 53 ices, including 20 knowncrystalline phases. We base such similarity comparison on the local environments that consist of atoms within a certain cutoff radius of a central atom. We reveal that liquid water explores the localenvironments of the diverse ice phases, by directly comparing the environments in these phases using general atomic descriptors, and also by demonstrating that a machine-learning potential trained on liquid water alone can predict the densities, the lattice energies, and vibrational properties of theices.…
Experiments and computer simulations have established that liquid water's surfaces can deviate in important ways from familiar bulk behavior. Even in the simplest case of an air-water interface, distinctive layering, orientational biases, and hydrogen bond arrangements have been reported, but an overarching picture of their origins and relationships has been incomplete. Here we show that a broad set of such observations can be understood through an analogy with the basal face of crystalline ice. Using simulations, we specifically demonstrate that water and ice surfaces share a set of structura…
Despite great efforts over the past 50 years, the simulation of water still presents significant challenges and open questions. At room temperature and pressure, the collective molecular interactions and dynamics of water molecules may form local structural arrangements that are non-trivial to classify. Here we employ a data-driven approach built on Smooth Overlap of Atomic Position (SOAP) that allow us to compare and classify how widely used classical models represent liquid water. Macroscopically, the obtained results are rationalized based on water thermodynamic observables. Microscopically…
A recent experiment [K. H. Kim, et al., Science 370, 978 (2020)] showed that it may be possible to detect a liquid-liquid phase transition (LLPT) in supercooled water by subjecting high density amorphous ice (HDA) to ultrafast heating, after which the sample reportedly undergoes spontaneous decompression from a high density liquid (HDL) to a low density liquid (LDL) via a first-order phase transition. Here we conduct computer simulations of the ST2 water model, in which a LLPT is known to occur. We subject various HDA samples of this model to a heating and decompression protocol that follows a…
Premelting describes the confluence of phenomena that are responsible for the stable existence of the liquid phase of matter in the solid region of its bulk phase diagram. Here we develop a theoretical description of the premelting of water ice contained in a porous matrix, made of a material with a melting temperature substantially larger than ice itself, to predict the amount of liquid water in the matrix at temperatures below its bulk freezing point. Our theory combines the interfacial premelting of ice in contact with the matrix, grain boundary melting in the ice, and impurity and curvatur…
Micropolar continua are shown to be the generalisation of the nematic liquid crystals through perspectives of order parameters, topological and geometrical considerations. Micropolar continua and nematic liquid crystals are recognised as the antipodals of $S^3$ and $S^2$ in projective geometry. We show that position-dependent rotational axial fields in kinematic micropolar continua can be considered as solutions of anisotropic Higgs fields, characterised by integers N. We emphasise that the identical integers N are topological invariants through homotopy classifications based on defects of ord…
We study the light scattering by localized quasi planar excitations of a Cholesteric Liquid Crystal known as spherulites. Due to the anisotropic optical properties of the medium and the peculiar shape of the excitations, we quantitatively evaluate the cross section of the axis-rotation of polarized light. Because of the complexity of the system under consideration, first we give a simplified, but analytical, description of the spherulite and we compare the Born approximation results in this setting with those obtained by resorting to a numerical exact solution. The effects of changing values o…
One of water's unsolved puzzles is the question of what determines the lowest temperature to which it can be cooled before freezing to ice. The supercooled liquid has been probed experimentally to near the homogeneous nucleation temperature TH{\approx}232 K, yet the mechanism of ice crystallization - including the size and structure of critical nuclei - has not yet been resolved. The heat capacity and compressibility of liquid water anomalously increase upon moving into the supercooled region according to a power law that would diverge at Ts{\approx}225 K,(1,2) so there may be a link between w…
In this paper we study the structure of the ice/vapor interface in the neighborhood of the triple point for the TIP4P/2005 model. We probe the fluctuations of the ice/film and film/vapor surfaces that separate the liquid film from the coexisting bulk phases at basal, primary prismatic and secondary prismatic planes. The results are interpreted using a coupled sine Gordon plus Interface Hamiltonian model. At large length-scales, the two bounding surfaces are correlated and behave as a single complex ice/vapor interface. For small length, on the contrary, the ice/film and film/vapor surfaces beh…
The well-known classical nucleation theory (CNT) for the free energy barrier towards formation of a nucleus of critical size of the new stable phase within the parent metastable phase fails to take into account the influence of other metastable phases having density/order intermediate between the parent metastable phase and the final stable phase. This lacuna can be more serious than capillary approximation or spherical shape assumption made in CNT. This issue is particularly significant in ice nucleation because liquid water shows rich phase diagram consisting of two (high and low density) li…
We characterized the structural and dynamical properties of the quasi-liquid layer (QLL) at the surface of ice by molecular dynamics simulations with a thermodynamically consistent water model. Our simulations show that for three low-index ice surfaces only the outermost molecular layer presents short-range and mid-range disorder and is diffusive. The onset temperature for normal diffusion is much higher than the glass temperature of supercooled water, although the diffusivity of the QLL is higher than that of bulk water at the corresponding temperature. The underlying subsurface layers impose…
Close to the triple point, the surface of ice is covered by a thin liquid layer (so-called quasi-liquid layer) which crucially impacts growth and melting rates. Experimental probes cannot observe the growth processes below this layer, and classical models of growth by vapor deposition do not account for the formation of premelting films. Here, we develop a mesoscopic model of liquid-film mediated ice growth, and identify the various resulting growth regimes. At low saturation, freezing proceeds by terrace spreading, but the motion of the buried solid is conveyed through the liquid to the outer…
Acoustic cavitation is known to trigger ice nucleation in supercooled water. Several competing and still debatable mechanisms have been proposed in the literature and are related to the pressure field in the vicinity of the bubble at the end of its collapse. Numerical simulations of the bubble dynamics show that during the bubble expansions in the bounces following the main collapse, the bubble core temperature reaches values far below 0 °C for time periods of about 500 ns. The water vapour present in the bubble during these time intervals explores the liquid and the solid region of the phase …
Water, in its three phases, is ubiquitous, and the surface properties of ice is important to clarifying the process of melting, as well as to various other fields, including geophysics. As such, the subject has been studied both theoretically and experimentally, for over a hundred years, while being an active field of research today. It has been established that surface melting, or premelting, exists below the melting point, and a `liquid-like layer' (LLL) exists on the surface of ice. Here, we use the surface thermal fluctuation spectra to study the properties of LLL, including its thickness,…
Liquid-liquid phase separation precedes crystallization in supercooled water-glycerol solutions
Stockholm University（斯德哥尔摩大学）；Saint Petersburg State University（圣彼得堡国立大学）；Deutsches Elektronen-Synchrotron DESY（德国电子同步加速器中心）；Technische Universität Bergakademie Freiberg（弗莱贝格矿业科技大学）；ESRF – The European Synchrotron（欧洲同步辐射装置）
Liquid salty micro-channels (brine) between growing ice platelets in sea ice are an important habitat for $CO_2$ - binding microalgaea with great impact on polar ecosystems. The structure formation of ice platelets is microscopically described and a phase field model is developed. The pattern formation during solidification of the two-dimensional interstitial liquid is considered by two coupled order parameters, the tetrahedricity as structure of ice and the salinity. The coupling and time-evolution of these order parameters are described by a consistent set of three model parameters. They det…
We derive a thermodynamically consistent model for phase change in sea ice by adding salt to the framework introduced by Penrose and Fife. Taking the salt entropy relative to the liquid water molar fraction provides a transparent mechanism for salt rejection under ice formation. We identify slow varying coordinates, including salt density relative to liquid water molarity weighted by latent heat, and use multiscale analysis to derive a quasi-equilibrium Stefan-type problem via a sharp interface scaling. The singular limit is under-determined and the leading order system is closed by imposing l…
