No Arabic abstract
Dielectric spectra (10^4-10^11 Hz) of water and ice at 0 {deg}C are considered in terms of proton conductivity and compared to each other. In this picture, the Debye relaxations, centered at 1/{tau}_W ~ 20 GHz (in water) and 1/{tau}_I ~ 5 kHz (in ice), are seen as manifestations of diffusion of separated charges in the form of H3O+ and OH- ions. The charge separation results from the self-dissociation of H2O molecules, and is accompanied by recombination in order to maintain the equilibrium concentration, N. The charge recombination is a diffusion-controlled process with characteristic lifetimes of {tau}_W and {tau}_I, for water and ice respectively. The static permittivity, {epsilon}(0), is solely determined by N. Both, N and {epsilon}(0), are roughly constant at the water-ice phase transition, and both increase, due to a slowing down of the diffusion rate, as the temperature is lowered. The transformation of the broadband dielectric spectra at 0 {deg}C with the drastic change from {tau}_W to {tau}_I is mainly due to an abrupt (by 0.4 eV) change of the activation energy of the charge diffusion.
Ice-water, water-vapor interfaces and ice surface are studied by molecular dynamics simulations with the SPC/E model of water molecules having the purpose to estimate the profiles of electrostatic potential across the interfaces. We have proposed a methodology for calculating the profiles of electrostatic potential based on a trial particle, which showed good agreement for the case of electrostatic potential profile of the water-vapor interface of TIP4P model calculated in another way. The measured profile of electrostatic potential for the pure ice-water interface decreases towards the liquid bulk region, which is in agreement with simulations of preferential direction of motion of Li$^{+}$ and F$^{-}$ solute ions at the liquid side of the ice-water interface. These results are discussed in connection with the Workman-Reynolds effect.
We investigate ice polyamorphism in the context of the two-dimensional Mercedes-Benz model of water. We find a first-order phase transition between a crystalline phase and a high-density amorphous phase. Furthermore we find a reversible transformation between two amorphous structures of high and low density; however we find this to be a continuous and not an abrupt transition, as the low-density amorphous phase does not show structural stability. We discuss the origin of this behavior and its implications with regard to the minimal generic modeling of polyamorphism.
The onset of rigidity in interacting liquids, as they undergo a transition to a disordered solid, is associated with a dramatic rearrangement of the low-frequency vibrational spectrum. In this letter, we derive scaling forms for the singular dynamical response of disordered viscoelastic networks near both jamming and rigidity percolation. Using effective-medium theory, we extract critical exponents, invariant scaling combinations and analytical formulas for universal scaling functions near these transitions. Our scaling forms describe the behavior in space and time near the various onsets of rigidity, for rigid and floppy phases and the crossover region, including diverging length and time scales at the transitions. We expect that these behaviors can be measured in systems ranging from colloidal suspensions to anomalous charge-density fluctuations of strange metals.
We compute the dielectric response of glasses starting from a microscopic system-bath Hamiltonian of the Zwanzig-Caldeira-Leggett type and using an ansatz from kinetic theory for the memory function in the resulting Generalized Langevin Equation. The resulting framework requires the knowledge of the vibrational density of states (DOS) as input, that we take from numerical evaluation of a marginally-stable harmonic disordered lattice, featuring a strong boson peak (excess of soft modes over Debye $simomega_{p}^{2}$ law). The dielectric function calculated based on this ansatz is compared with experimental data for the paradigmatic case of glycerol at $Tlesssim T_{g}$. Good agreement is found for both the reactive (real part) of the response and for the $alpha$-relaxation peak in the imaginary part, with a significant improvement over earlier theoretical approaches, especially in the reactive modulus. On the low-frequency side of the $alpha$-peak, the fitting supports the presence of $sim omega_{p}^{4}$ modes at vanishing eigenfrequency as recently shown in [Phys. Rev. Lett. 117, 035501 (2016)]. $alpha$-wing asymmetry and stretched-exponential behaviour are recovered by our framework, which shows that these features are, to a large extent, caused by the soft boson-peak modes in the DOS.
Crystallization from a supercooled liquid initially proceeds via the formation of a small solid embryo (nucleus), which requires surmounting an activation barrier. This phenomenon is most easily studied by numerical simulation, using specialized biased-sampling techniques to overcome the limitations imposed by the rarity of nucleation events. Here, I focus on the barrier to homogeneous ice nucleation in supercooled water, as represented by the monatomic-water model, which in the bulk exhibits a complex interplay between different ice structures. I consider various protocols to identify solidlike particles on a computer, which perform well enough for the Lennard-Jones model, and compare their respective impact on the shape and height of the nucleation barrier. It turns out that the effect is stronger on the nucleus size than on the barrier height. As a by-product of the analysis, I determine the structure of the nucleation cluster, finding that the relative amount of ice phases in the cluster heavily depends on the method used for classifying solidlike particles. Moreover, the phase which is most favored during the earlier stages of crystallization may happen, depending on the nucleation coordinate adopted, to be different from the stable polymorph. Therefore, the quality of a reaction coordinate cannot be assessed simply on the basis of the barrier height obtained. I explain how this outcome is possible and why it just points out the shortcoming of collective variables appropriate to simple fluids in providing a robust method of particle classification for monatomic water.