The freezing of water to ice is fundamentally important to fields as diverse as cloud formation to cryopreservation. At ambient conditions, ice is considered to exist in two crystalline forms: stable hexagonal ice and metastable cubic ice. Using X-ray diffraction data and Monte Carlo simulations, we show that ice that crystallizes homogeneously from supercooled water is neither of these phases. The resulting ice is disordered in one dimension and therefore possesses neither cubic nor hexagonal symmetry and is instead composed of randomly stacked layers of cubic and hexagonal sequences. We refer to this ice as stacking-disordered ice I. Stacking disorder and stacking faults have been reported earlier for metastable ice I, but only for ice crystallizing in mesopores and in samples recrystallized from high-pressure ice phases rather than in water droplets. Review of the literature reveals that almost all ice that has been identified as cubic ice in previous diffraction studies and generated in a variety of ways was most likely stacking-disordered ice I with varying degrees of stacking disorder. These findings highlight the need to reevaluate the physical and thermodynamic properties of this metastable ice as a function of the nature and extent of stacking disorder using well-characterized samples.

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We employ the cleaving approach to calculate directly the ice Ih-water interfacial free energy for the simple models of water, TIP4P, TIP4P-Ew, and TIP5P-E, with full electrostatic interactions evaluated via the Ewald sums. The results are in good agreement with experimental values, but lower than previously obtained for TIP4P-Ew and TIP5P-E by indirect methods. We calculate the interfacial free energies for basal, prism, and {112̅0} interfaces and find that the anisotropy of the TIP5P-E model is different from that of the TIP4P models. The effect of including full electrostatic interactions is determined to be smaller than 10% compared to the water models with damped Coulomb interactions, which indicates that the value of the ice-water interfacial free energy is determined predominantly by the short-range packing interaction between water molecules. We also observe a strong linear correlation between the interfacial free energy and the melting temperature of different water models.

We model cyclic voltammetry experiments on supported lipid films where a non-trivial dependence of the capacitance on the applied voltage is observed. Previously, based on a mean-field treatment of the Flory-Huggins type, under the assumption of strongly screened electrostatic interactions, it has been hypothesized that peaks in the capacitance-vs-voltage profiles correspond to a sequence of structural or phase transitions within the interface. To examine this hypothesis, in this study we use both mean-field calculations and Monte Carlo simulations where the electrostatic effects due to the varying electric potential and the presence of salt are accounted for explicitly. Our main focus is on the structure of the film and the desorption-readsorption phenomena. These are found to be driven by a strong competition for the progressively charged-up (hydrophobic) surface between lipid hydrocarbon tails and the electrode counterions (cations). As the surface charge density is raised, the following phase phenomena within the interface are clearly observed: (i) a gradual displacement of the monolayer from the surface by the counterions, leading to complete monolayer desorption and formation of an electric double layer by the surface, (ii) a transformation of the monolayer into a bilayer upon its desorption, (iii) in the case of zwitterionic (or strongly polar) lipid head groups, the desorption is followed by the bilayer readsorption to the electrode via interaction with the electric double layer and release of the excess counterions into the bulk solution. We argue then that the voltammetry peaks are associated with a stepwise process of formation of layers of alternating charge: electric double layer -upon film desorption, triple or multi-layer -upon film readsoption. * Corresponding author, E-mail: a.brukhno@leeds.ac.uk † Also known as Andrei V. Broukhno 1 arXiv:1007.3004v2 [cond-mat.soft]