Liquid to quasicrystal transition in bilayer water

The phase behavior of confined water is a topic of intense and current interest due to its relevance in biology, geology, and materials science. Nevertheless, little is known about the phases that water forms even when confined in the simplest geometries, such as water confined between parallel surfaces. Here we use molecular dynamics simulations to compute the phase diagram of two layers of water confined between parallel non hydrogen bonding walls. This study shows that the water bilayer forms a dodecagonal quasicrystal, as well as two previously unreported bilayer crystals, one tiled exclusively by pentagonal rings. Quasicrystals, structures with long-range order but without periodicity, have never before been reported for water. The dodecagonal quasicrystal is obtained from the bilayer liquid through a reversible first-order phase transition and has diffusivity intermediate between that of the bilayer liquid and ice phases. The water quasicrystal and the ice polymorphs based on pentagons are stabilized by compression of the bilayer and are not templated by the confining surfaces, which are smooth. This demonstrates that these novel phases are intrinsically favored in bilayer water and suggests that these structures could be relevant not only for confined water but also for the wetting and properties of water at interfaces.     

限制在疏水板中的新的六边形-四边形三层冰结构

对限制在两个光滑的疏水板间的水进行了分子动力学模拟,观察到了两种晶体结构,都满足冰规则．在1GPa的压强和1．0nm的板间距下获得的新的冰相是平坦的六边形-四边形三层冰．在此结构中,靠近板的两层（外层）中的水分子形成六边形环,中间层的水分子形成四边形环．对于外层的水分子,其四个氢键中的三个在同一层中,另一个氢键与中间层连接．对于中间层的水分子,四个氢键中的两个在同。层中,而另外两个氢键与两个不同的外层相连．虽然三层的形状不同,但其面密度却接近相等．另一种结构是在0．8nm的板问距和100MPa的侧向压下获得的平坦的六边形双层冰．模拟中的相变既有一阶相变,也有连续相变．     

A reexamination of the ice III/IX hydrogen bond ordering phase transition

Ice III is a hydrogen bond disordered crystal which when cooled 1 K / min or faster transforms to an antiferroelectric hydrogen bond ordered structure, ice IX. Throughout its region of stability, experiments indicate that the H bonds in ice III are, in fact, partially ordered, i.e., some proton arrangements are preferred. In addition, there has been evidence that the structure of ice IX retains some residual disorder after the transition. Diffraction experiments and calorimetry apparently conflict with regard to the degree of ordering at the ice III/IX transition. Mean field statistical mechanical theories have been used to link partial occupations from diffraction data with thermodynamics. In this work, we investigate the ice III/IX proton ordering phase transition using electronic density functional theory calculations for small unit cells, extended to simulate the phase transition in a large unit cell using graph invariants. In agreement with experiment, we observe partial ordering over a wide range of temperatures as ice III transforms to partially disordered ice IX, near 126 K, which becomes fully ordered at lower temperatures. We compare our results from full statistical mechanical simulations with mean field models, finding small errors for the low-temperature ice IX phase and much larger errors for the high-temperature ice III phase. The failure of mean field theories may explain the apparent conflict between diffraction experiments and calorimetry.     

Dynamics of a network of hydrogen bonds upon water electrocrystallization

Computer simulation is employed to study the dynamics of a network of hydrogen bonds and the structural properties of water placed between graphene layers. The presence of the graphene walls has been shown to substantially affect the water phase diagram. Glass transition processes are observed in the system, and liquid water completely passes to an amorphous state. Moreover, it has been established that the imposition of an external electric field with strength E ≥ 0.5 V/Å on the system subjected to increased pressure results in structural ordering of water. It has been found that water located between graphene layers is transformed into Ic cubic ice. The electrocrystallization of water has been shown to substantially change the dynamics of the network of hydrogen bonds.     

Strong stretching theory for diblock copolymers in thin films under application of electric fields

We investigate the microphases of asymmetric AB diblock copolymers confined to thin films in the strong segregation limit under the application of electric fields. We evaluate the free energy of a given set of possible phases and present phase diagrams for diblock copolymers with a cylindrical bulk phase in dependence of the film thickness and the attraction between the confining walls and the A or B monomers. This is done for different field strengths and volume fractions. We find that with increasing field strength structures show a preference for alignment with the field. The alignment is stronger when the permittivity of the minority monomer is larger than that of the majority monomer. Depending on the strength of the wall potential and the film thickness, the walls can become completely wetted by the minority monomer.     

Magnetic freezing of confined water

We report results from molecular dynamic simulations of the freezing transition of liquid water in the nanoscale hydrophobic confinement under the influence of a homogeneous external magnetic field of 10 T along the direction perpendicular to the parallel plates. A new phase of bilayer crystalline ice is obtained at an anomalously high freezing temperature of 340 K. The water-to-ice translation is found to be first order. The bilayer ice is built from alternating rows of hexagonal rings and rhombic rings parallel to the confining plates, with a large distortion of the hydrogen bonds. We also investigate the temperature shifts of the freezing transition due to the magnetic field. The freezing temperature, below which the freezing of confined water occurs, shifts to a higher value as the magnetic field enhances. Furthermore, the temperature of the freezing transition of confined water is proportional to the denary logarithm of the external magnetic field.     

Phase transition of nanotube-confined water driven by electric field

The effects of electric field on the phase behaviors of water encapsulated in a thick single-walled carbon nanotube (SWCNT) (diameter = 1.2 nm) have been studied by performing extensive molecular dynamics simulations at atmospheric pressure. We found that liquid water can freeze continuously into either pentagonal or helical solidlike ice nanotube in SWCNT, depending on the strengths of the external electric field applied along the tube axis. Remarkably, the helical one is new ice phase which was not observed previously in the same size of SWCNT in the absence of electric field. Furthermore, a discontinuous solid-solid phase transition is observed between pentagonal and helical ice nanotubes as the strengths of the external electric field changes. The mechanism of electric-field-induced phase transition is discussed. The dependence of ice structures on the chiralities of SWCNTs is also investigated. Finally, we present a phase diagram of confined water in the electric field-temperature plane.     

The polymorphism of ice: five unresolved questions

Our recent discovery of three new phases of ice has increased the total number of known distinct polymorphs of ice to fifteen. In this Perspective article, we give a brief account of previous work in the field, and discuss some of the particularly interesting open questions that have emerged from recent studies. These include (i) the effectiveness of acid and base dopants to enable hydrogen-ordering processes in the ices, (ii) the comparison of the calorimetric data of some of the crystalline phases of ice and low-density amorphous ice, (iii) the disagreement between the experimental ice XV structure and computational predictions, (iv) the incompleteness of some of the hydrogen order/disorder pairs and (v) the new frontiers at the high and negative pressure ends of the phase diagram.     

Orientational orders of small anisotropic molecules confined in slit pores

Based on a constant-pressure Monte Carlo molecular simulation, we have studied orientationally ordered transitions of small anisotropic molecules confined in two parallel hard walls. These molecules are modeled by the hard Gaussian overlap model. The molecular elongations of the chosen molecules are so small that the molecules cannot form stable liquid-crystal (LC) phases in the bulk. But in the slit pores, we found, while the distance between two walls of the pores decreases to the molecular scale, an orientationally ordered phase can form. It shows that even hard confining surfaces favor the alignment of the small anisotropic molecules. Thus we conclude that the required molecular elongation for forming LC phases will decrease in confinement. Our results indicate that some non-LC small molecules may form stable LC phases due to the inducement of confining surfaces.     

Assessment of density functional theory to calculate the phase transition pressure of ice

To assess the accuracy of density functional theory (DFT) methods in describing hydrogen bonding in condensed phases, we benchmarked their performance in describing phase transitions among different phases of ice. We performed DFT calculations of ice for phases Ih, II, III, VI and VII using BLYP, PW91, PBE, PBE-D, PBEsol, B3LYP, PBE0, and PBE0-D, and compared the calculated phase transition pressures between Ih-II, Ih-III, II-VI, and VI-VII with the 0 K experimental values of Whalley [J. Chem. Phys., 1984, 81, 4087]. From the geometry optimization of many different candidates, we found that the most stable proton orientation as well as the phase transition pressure does not show much functional dependence for the generalized gradient approximation and hybrid functionals. Although all these methods overestimated the phase transition pressure, the addition of van der Waals (vdW) correction using PBE-D and PBE0-D reduced the transition pressure and improved the agreement for Ih-II. On the other hand, energy ordering between VI and VII reversed and gave an unphysical negative transition pressure. Binding energy profiles of a few conformations of water dimers were calculated to understand the improvement for certain transitions and failures for others with the vdW correction. We conclude that vdW dispersion forces must be considered to accurately describe the hydrogen bond in many different phases of ice, but the simple addition of the R(-6) term with a small basis set tends to over stabilize certain geometries giving unphysical ordering in the high density phases.     

Water confined in nanotubes and between graphene sheets: a first principle study

Water confined at the nanoscale has been the focus of numerous experimental and theoretical investigations in recent years, yet there is no consensus on such basic properties as diffusion and the nature of hydrogen bonding (HB) under confinement. Unraveling these properties is important to understand fluid flow and transport at the nanoscale, and to shed light on the solvation of biomolecules. Here we report on a first principle, computational study focusing on water confined between prototypical nonpolar substrates, i.e., single-wall carbon nanotubes and graphene sheets, 1-2.5 nm apart. The results of our molecular dynamics simulations show the presence of a thin, interfacial liquid layer (approximately 5 A) whose microscopic structure and thickness are independent of the distance between confining layers. The properties of the HB network are very similar to those of the bulk outside the interfacial region, even in the case of strong confinement. Our findings indicate that the perturbation induced by the presence of confining media is extremely local in liquid water, and we propose that many of the effects attributed to novel phases under confinement are determined by subtle electronic structure rearrangements occurring at the interface with the confining medium.     

Low density mesostructures of confined dipolar particles in an external field

Mesostructures formed by dipolar particles confined between two parallel walls and subjected to an external field are studied by Monte Carlo simulations. The main focus of the work is the structural behavior of the Stockmayer fluid in the low density regime. The dependence of cluster thickness and ordering is estimated as a function of density and wall separation, the two most influential parameters, for large dipole moments and high field strengths. The great sensitivity of the structure to details of the short-range part of the interactions is pointed out. In particular, the attractive part of the Lennard-Jones potential is shown to play a major role in driving chain aggregation. The effect of confinement, evaluated by comparison with results for a bulk system, is most pronounced for a short range hard sphere potential. No evidence is found for a novel "gel-like" phase recently uncovered in low density dipolar colloidal suspensions [A. K. Agarwal and A. Yethiraj, Phys. Rev. Lett. 102, 198301 (2009)].     

Resolving the aluminum ordering in aluminosilicates by a combined experimental/theoretical study of 27Al electric field gradients

The discrimination between atomic species in light-element materials is a challenging question. An archetypal example is the resolution of the Al/Si ordering in aluminosilicates. Only an average long-range order can be deduced from powder X-ray or neutron diffraction, while magic-angle-spinning NMR provides an accurate picture of the short-range order. The long- and short-range orders thus obtained usually differ, hence raising the question of whether the difference between local and extended orders is intrinsic or caused by the difficulty of obtaining an accurate picture of the long-range order from diffraction techniques. In this communication we resolve this question for the monoclinic phases of BaAl2Si2O8 and SrAl2Si2O8 on the basis of 27Al NMR measurements and ab initio simulation of electric field gradient. Although the long- and short-range orders deduced from our XRD and NMR experiments differ, they become similar when the XRD atomic positions are optimized by ab initio electronic structure calculations.     

Calculation of near-edge x-ray-absorption fine structure at finite temperatures: spectral signatures of hydrogen bond breaking in liquid water

We calculate the near-edge x-ray-absorption fine structure of H(2)O in the gas, hexagonal ice, and liquid phases using heuristic density-functional based methods. We present a detailed comparison of our results with experiment. The differences between the ice and water spectra can be rationalized in terms of the breaking of hydrogen bonds around the absorbing molecule. In particular the increase in the pre-edge absorption feature from ice to water is shown to be due to the breaking of a donor hydrogen bond. We also find that in water approximately 19% of hydrogen bonds are broken.     

Phase separation in thin films of polymer blends: The influence of symmetric boundary conditions

Using nuclear reaction analysis composition‐depth profiling, we investigate the influence of symmetric/asymmetric confining walls on the equilibrium configuration of thin films of phase‐separated polymer blends. Depth profiles of samples annealed under symmetric boundary conditions show a laterally averaged concentration, while samples confined by nonsymmetric walls show (as in earlier studies) clear separation into two thin layers of coexisting phases. This suggests that for phase separation under symmetric boundary conditions the interface between the two phases is orthogonal to the sample plane, in line with recent theoretical discussion. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 831–837, 2000     

Crystallization in thin liquid films induced by shear

It is known that the thin-film structure of confined fluids and solids can be changed when the confining surfaces are sheared. Positional and orientational short- or long-range reordering can occur that often have no bulk counterparts. These multilayer, monolayer, or even sub-monolayer effects are important for understanding adhesion and friction processes, but they have proved difficult to measure, partly due to a lack of experimental techniques and partly to their apparent subtle dependence on many experimental parameters. Here we report the use of shear measurements and "optical absorption spectroscopy" in the surface forces apparatus to measure a shear-induced phase transition of an anisotropic (dye) molecule confined between two shearing mica surfaces in aqueous solution. Our studies on the shear-induced ordering and friction forces of highly anisotropic cyanine dye molecules in thin water films show only a weak effect of molecular anisotropy on shear-induced ordering, friction forces, and the onset of shear-induced crystallization, although dramatic changes do occur when the confined molecules ultimately crystallize.     

Polarizable model of water with field-dependent polarization

The polarizable charge-on-spring model of water with three Gaussian charges developed by the present authors [A. Baranyai and P. T. Kiss, J. Chem. Phys. 133, 144109 (2010)] was studied. We introduced an analytic function for the polarizability in terms of the local electric field. Following theoretical suggestions, the polarizability decreases from its experimental gas-phase value, in our approach, toward a high-field threshold. Using this modified polarizability, we reparameterized the model by calculating its dielectric constant and obtained good estimates of density and internal energy for ambient water, hexagonal ice, and water cluster properties. Mimicked by the new model, we studied liquid water under the impact of homogeneous static electric field in the rage of 0-2.5 V/?. Both the density and the average dipole moment increase with the strength of the electric field. However, the internal energy shows a minimum at ~0.35 V/?. At this field strength, the model starts ordering into a crystal structure. At higher fields the liquid forms a crystalline structure which is a special version of cubic ice.     

Experimental study of structure and dynamics in a monolayer of paramagnetic colloids confined by parallel hard walls

We study the structural and dynamical properties of paramagnetic colloidal spheres interacting as repulsive dipoles in two dimensions and confined between parallel hard walls. We observed that the structure and dynamics of the self-assembled colloids are strongly dependent upon the width of the confining channel. The system exhibits re-entrant behavior as a function of the channel width, transitioning from solid-like to liquid-like repeatedly in excellent agreement with simulation results. For large channels, an ordered layered structure self-assembles near the walls, but this local structure is not commensurate with the bulk structure, leading to localized stable defects.     

A computer simulation of the mechanism of self-conservation of gas hydrates

Local density profiles and local component pressure profiles were obtained for two model systems containing methane hydrate and ice by molecular dynamics simulation. The ice matrix with methane hydrate clusters inserted into it was shown to be stable at normal pressure and even at a temperature higher than the temperature of methane hydrate dissociation. Calculations showed that the pressure in such a methane hydrate cluster inserted into ice was higher than in the ice phase. There were, however, no strong structure distortions because of the formation of a network of strong hydrogen bonds between the hydrate and ice phases.     

Prediction of a phase transition to a hydrogen bond ordered form of ice VI

Ice VI is a hydrogen bond disordered crystal over its known region of stability. In this work, we predict that ice VI will transform into a hydrogen bond ordered phase near 108 K, and have identified the likely low-temperature phase as ferroelectric (space group Cc) with an antiferroelectric structure (space group P2(1)2(1)2(1)) close by in energy. Electronic density functional theory calculations provide input to our calculations, which are extended to cells large enough for statistical simulations by using graph invariants. A significant decrease in the configurational entropy is predicted as hydrogen bonds exhibit partial order above the transition, provided that the hydrogen bonds can equilibrate on an experimental time scale. Conversely, partial disorder is predicted at temperatures below the transition. Although some evidence for ordering of ice VI has been observed in experiments, a low-temperature proton ordered phase has not been identified experimentally.