RESUMEN

We examine an algorithm for the creation of proton-disordered ice cells based on a simulated-annealing (SA) scheme for molecular orientations. Application to defect-free ice Ih, a clathrate-hydrate structure, and a random polycrystalline ice Ih sample demonstrates the SA technique to be effective, attaining maximum HB connectivity using relatively short cooling simulations, thus serving as an alternative method for those cases in which the application of topology-based methods is inhibited.

RESUMEN

Superionic (SI) water ices-high-temperature, high-pressure phases of water in which oxygen ions occupy a regular crystal lattice whereas the protons flow in a liquid-like manner-have attracted a growing amount of attention over the past few years, in particular due to their possible role in the magnetic anomalies of the ice giants Neptune and Uranus. In this paper, we consider the calculation of the free energies of such phases, exploring hybrid reference systems consisting of a combination of an Einstein solid for the oxygen ions occupying a crystal lattice and a Uhlenbeck-Ford potential for the protonic fluid that avoids irregularities associated with possible particle overlaps. Applying this approach to a recent neural-network potential-energy landscape for SI water ice, we compute Gibbs free energies as a function of temperature for the SI fcc and liquid phases to determine the melting temperature Tm at 340 GPa. The results are consistent with previous estimates and indicate that the entropy difference between both phases is comparatively small, in particular due to the large amplitude of vibration of the oxygen ions in the fcc phase at the melting temperature.

RESUMEN

The mass transport properties along dislocation cores in hcp ^{4}He are revisited by considering two types of edge dislocations as well as a screw dislocation, using a fully correlated quantum simulation approach. Specifically, we employ the zero-temperature path-integral ground state (PIGS) method together with ergodic sampling of the permutation space to investigate the fundamental dislocation core structures and their off-diagonal long-range order properties. It is found that the Bose-Einstein condensate fraction of such defective ^{4}He systems is practically null (≤10^{-6}), just as in the bulk defect-free crystal. These results provide compelling evidence for the absence of intrinsic superfluidity in dislocation cores in hcp ^{4}He and challenge the superfluid dislocation-network interpretation of the mass-flux-experiment observations, calling for further experimental investigation.

Asunto(s)

RESUMEN

Due to their potential role in the peculiar geophysical properties of the ice giants Neptune and Uranus, there has been a growing interest in superionic (SI) phases of water ice. So far, however, little attention has been given to their mechanical properties, even though plastic deformation processes in the interiors of planets are known to affect long-term processes, such as plate tectonics and mantle convection. Here, using density functional theory calculations and machine learning techniques, we assess the mechanical response of high-pressure/temperature solid phases of water in terms of their ideal shear strength (ISS) and dislocation behavior. The ISS results are well described by the renormalized Frenkel model of ideal strength and indicate that the SI ices are expected to be highly ductile. This is further supported by deep neural network molecular dynamics simulations for the behavior of lattice dislocations for the SI face-centered cubic (fcc) phase. Dislocation velocity data indicate effective shear viscosities that are orders of magnitude smaller than that of Earth's lower mantle, suggesting that the plastic flow of the internal icy layers in Neptune and Uranus may be significantly faster than previously foreseen.

RESUMEN

The anomalous increase in compressibility and heat capacity of supercooled water has been attributed to its structural transformation of into a four-coordinated liquid. Experiments revealed that κT and Cp peak at TWthermo ≈ 229 K [Kim et al. Science 2017, 358, 1589; Pathak et al. Proc. Natl. Acad. Sci. 2021, 118, e2018379118]. Recently, a pulsed heating procedure (PHP) was employed to interrogate the structure of water, reporting a steep increase in tetrahedrality around TWPHP = 210 ± 3 K [Kringle et al. Science 2020, 369, 1490]. This discrepancy questions whether water structure and thermodynamics are decoupled, or if the shift in TW is an artifact of PHP. Here we implement PHP in molecular simulations. We find that the stationary states captured at the bottom of the pulse are not representative of the thermalized liquid or its inherent structure. Our analysis reveals a temperature-dependent distortion that shifts TWPHP to ∼20 K below TWthermo. We conclude that 2 orders of magnitude faster rates are required to sample water's inherent structure with PHP.

RESUMEN

In this paper, we present an overview of crystal imperfections in ice Ih. Due to its molecular nature, the fundamental asymmetry of the hydrogen bond, and proton disorder, crystal defects in this condensed form of water reveal a complexity not usually seen in atomic crystalline solids. The discussion is organized in terms of the spatial extent of the defects. We start with zero-dimensional imperfections such as the molecular vacancy and interstitial, Bjerrum, and ionic defects, as well as possible defect complexes that can be formed from them. Subsequently, we turn to the properties of dislocations, which are the one-dimensional disturbances that carry plastic deformation in crystalline solids. Finally, we discuss two-dimensional defects such as stacking faults and grain boundaries and discuss to what extent the latter are similar to other interfaces in ice Ih such as the free surface. We conclude with an outlook at the road ahead, discussing future challenges toward understanding the role of crystal defects in the macroscopic behavior of ice Ih.

RESUMEN

We consider rapid cooling processes in classical, three-dimensional, purely repulsive binary mixtures in which an initial infinite-temperature (ideal-gas) configuration is instantly quenched to zero temperature. It is found that such systems display two kinds of ordering processes, the type of which can be controlled by tuning the interactions between unlike particles. While strong inter-species repulsion leads to chemical ordering in terms of an unmixing process, weak repulsion gives rise to spontaneous crystallization, maintaining chemical homogeneity. This result indicates the existence of a transition in the topography of the underlying potential-energy landscape as the intra-species interaction strength is varied. Furthermore, the dual-type behavior appears to be universal for repulsive pair-interaction potential-energy functions in general, with the propensity for the crystallization process being related to their behavior in the neighborhood of zero separation.

RESUMEN

We assess the elastic stiffness constants of hexagonal proton-disordered ice Ih as described by density-functional theory calculations. Specifically, we compare the results for a set of nine exchange-correlation functionals, including standard generalized-gradient approximations (GGAs), the strongly constrained and appropriately normed (SCAN) metaGGA functional, and a number of dispersion-corrected versions based on the van der Waals (vdW) and VV10 schemes. Compared to the experimental data, all functionals predict an excessively stiff response to tensile and compressive distortions, as well as shear deformations along the basal plane, with the SCAN metaGGA functional displaying the largest deviations as compared to the experimental values. These discrepancies are found to correlate with underestimates of inter-molecular distances, on the one hand, and overestimates of intra-molecular separations, on the other. The inclusion of non-local vdW corrections according to the vdW approach generally improves these structural parameters and softens the elastic response functions compared to their parent GGA functionals. The dispersion-corrected SCAN-rVV10 functional, however, acts in the opposite direction, further worsening the comparison to experiment. In this view, it appears useful that the database employed to gauge the quality of exchange-correlation functionals for water includes an assessment of their elastic response of ice Ih and possibly other crystalline phases.

RESUMEN

Using molecular dynamics simulations, we compute the elastic constants of ice Ih for a set of 8 frequently used semi-empirical potentials for water, namely, the rigid-molecule SPC/E, TIP4P, TIP4P2005, TIP4P/Ice, and TIP5P models, the flexible-molecule qTIP4P/Fw and SPC/Fw models, and the coarse-grained atomic mW potential. In quantitative terms, the mW description gives values for the individual stiffness constants that are closest to the experiment, whereas the explicit-proton models display substantial discrepancies. On the other hand, in contrast to all explicit-proton potentials, the mW model is unable to reproduce central qualitative trends such as the anisotropy in Young's modulus and the shear modulus. This suggests that the elastic behavior of ice Ih is closely related to its molecular nature, which has been coarse-grained out in the mW model. These observations are consistent with other recent manifestations concerning the limitations of the mW model in the description of mechanical properties of ice Ih.

RESUMEN

Using molecular dynamics simulations, we assess the uniaxial deformation response of ice I h as described by two popular water models, namely, the all-atom TIP4P/Ice potential and the coarse-grained mW model. In particular, we investigate the response to both tensile and compressive uniaxial deformations along the [0001] and [ 0 1 ¯ 10 ] crystallographic directions for a series of different temperatures. We classify the respective failure mechanisms and assess their sensitivity to strain rate and cell size. While the TIP4P/Ice model fails by either brittle cleavage under tension at low temperatures or large-scale amorphization/melting, the mW potential behaves in a much more ductile manner, displaying numerous cases in which stress relief involves the nucleation and subsequent activity of lattice dislocations. Indeed, the fact that mW behaves in such a malleable manner even at strain rates that are substantially higher than those applied in typical experiments indicates that the mW description of ice I h is excessively ductile. One possible contribution to this enhanced malleability is the absence of explicit protons in the mW model, disregarding the fundamental asymmetry of the hydrogen bond that plays an important role in the nucleation and motion of lattice dislocations in ice I h .

RESUMEN

Using ab initio and classical molecular dynamics simulations, we study pre-melting phenomena in pristine coincident-site-lattice grain boundaries (GBs) in proton-disordered hexagonal ice Ih at temperatures just below the melting point Tm. Concerning pre-melt-layer thicknesses, the results are consistent with the available experimental estimates for low-disorder impurity-free GBs. With regard to molecular mobility, the simulations provide a key new insight: the translational motion of the water molecules is found to be subdiffusive for time scales from ∼10 ns up to at least 0.1 µs. Moreover, the fact that the anomalous diffusion occurs even at temperatures just below Tm where the bulk supercooled liquid still diffuses normally suggests that it is related to the confinement of the GB pre-melt layers by the surrounding crystalline environment. Furthermore, we show that this behavior can be characterized by continuous-time random walk models in which the waiting-time distributions decay according to power-laws that are very similar to those describing dynamics in glass-forming systems.

RESUMEN

Using molecular dynamics simulations and nonequilibrium thermodynamic-integration techniques we compute the Helmholtz free energies of the body-centered-cubic (bcc), face-centered-cubic (fcc), hexagonal close-packed, and fluid phases of the Uhlenbeck-Ford model (UFM) and use the results to construct its phase diagram. The pair interaction associated with the UFM is characterized by an ultrasoft, purely repulsive pair potential that diverges logarithmically at the origin. We find that the bcc and fcc are the only thermodynamically stable crystalline phases in the phase diagram. Furthermore, we report the existence of two reentrant transition sequences as a function of the number density, one featuring a fluid-bcc-fluid succession and another displaying a bcc-fcc-bcc sequence near the triple point. We find strong resemblances to the phase behavior of other soft, purely repulsive systems such as the Gaussian-core model (GCM), inverse-power-law, and Yukawa potentials. In particular, we find that the fcc-bcc-fluid triple point and the phase boundaries in its vicinity are in good agreement with the prediction supplied by a recently proposed corresponding-states principle [J. Chem. Phys. 134, 241101 (2011)JCPSA60021-960610.1063/1.3605659; Europhys. Lett. 100, 66004 (2012)EULEEJ0295-507510.1209/0295-5075/100/66004]. The particularly strong resemblance between the behavior of the UFM and GCM models are also discussed.

RESUMEN

The Uhlenbeck-Ford (UF) model was originally proposed for the theoretical study of imperfect gases, given that all its virial coefficients can be evaluated exactly, in principle. Here, in addition to computing the previously unknown coefficients B11 through B13, we assess its applicability as a reference system in fluid-phase free-energy calculations using molecular simulation techniques. Our results demonstrate that, although the UF model itself is too soft, appropriately scaled Uhlenbeck-Ford (sUF) models provide robust reference systems that allow accurate fluid-phase free-energy calculations without the need for an intermediate reference model. Indeed, in addition to the accuracy with which their free energies are known and their convenient scaling properties, the fluid is the only thermodynamically stable phase for a wide range of sUF models. This set of favorable properties may potentially put the sUF fluid-phase reference systems on par with the standard role that harmonic and Einstein solids play as reference systems for solid-phase free-energy calculations.

RESUMEN

The water-solvated excess electron (EE) is a key chemical agent whose hallmark signature, its asymmetric optical absorption spectrum, continues to be a topic of debate. While nearly all investigation has focused on the liquid-water solvent, the fact that the crystalline-water solvated EE shows a very similar visible absorption pattern has remained largely unexplored. Here, we present spin-polarized density-functional theory calculations subject to periodic boundary conditions of the interplay between an EE and a number of intrinsic lattice defects in ice Ih. Our results show that the optical absorption signatures in the presence of three unsaturated hydrogen bonds (HB) are very similar to those observed experimentally. Its low-energy side can be attributed to transitions between the EE ground state and a single localized excited level, in a picture that is different from that for the liquid solvent, where this portion has been associated with hydrogen-like s → p excitations. The blue tail, on the other hand, relates to transitions between the EE ground state and delocalized excited states, which is in line with the bound-to-continuum transition interpretations for the EE in liquid water. Finally, we find that, depending on the number of dangling HBs participating in the EE trap, its charge density may spontaneously break the spin degeneracy through exchange interactions with the surrounding electrons, displaying the many-electron quantum nature of the EE problem in ice Ih.

RESUMEN

We discuss the role of nuclear quantum fluctuations in ice Ih, focusing on the hydrogen-bond (HB) structure and the molecular dipole-moment distribution. For this purpose we carry out DFT-based first-principles molecular dynamics and path-integral molecular dynamics simulations at T = 100 K. We analyze the HB structure in terms of a set of parameters previously employed to characterize molecular structures in the liquid phase and compute the molecular dipole moments using the maximally-localized Wannier functions. The results show that the protons experience very large digressions driven by quantum fluctuations, accompanied by major rearrangements in the electronic density. As a result of these protonic quantum fluctuations the molecular dipole-moment distribution is substantially broadened as well as shifted to a larger mean value when compared to the results obtained when such fluctuations are neglected. In terms of dielectric constants, the reconciliation between the greater mean dipole moment and experimental indications that the dielectric constant of H2O ice is lower than that of D2O ice would indicate that the topology of the HB network is sensitive to protonic quantum fluctuations.

Asunto(s)

RESUMEN

Using path-integral Monte Carlo simulations, we compute the ideal shear strength (ISS) on the basal plane of hcp (4)He. The failure mode upon reaching the ISS limit is characterized by the homogeneous nucleation of a stacking fault and it is found to be anisotropic, consistent with Schmid's law of resolved shear stress. Comparing the ISS of hcp (4)He to a large set of classical crystals shows that it closely fits the approximately universal modified Frenkel model of ideal strength. In addition to giving quantitative stress levels for the homogeneous nucleation of extended defects in hcp (4)He, our findings lend support to assumptions in the literature that inherently classical models remain useful for the description of mechanical behavior in quantum crystals.

RESUMEN

Using molecular dynamics simulations we analyze the dynamics of two atomic liquids that display a liquid-liquid phase transition (LLPT): Si described by the Stillinger-Weber potential and Ga as modeled by the modified embedded-atom model. In particular, our objective is to investigate the extent to which the presence of a dip in the self-intermediate scattering function is a manifestation of an excess of vibrational states at low frequencies and may be associated with a fragile-to-strong transition (FTST) across the LLPT, as suggested recently. Our results suggest a somewhat different picture. First, in the case of Ga we observe the appearance of an excess of vibrational states at low frequencies, even in the absence of the appearance of a dip in the self-intermediate scattering function across the LLPT. Second, studying the behavior of the shear viscosities traversing the LLPTs we find that both substances are fragile in character above and below their respective LLPT temperatures. Instead of a FTST in an absolute sense these findings are more in line with a view in which the LLPTs are accompanied by a transition from a more fragile to a less fragile liquid. Furthermore, we do not find this transition to correlate with the presence of a dip in the intermediate scattering function.

RESUMEN

We investigate the uptake of HCl and HF at lattice vacancies in ice Ih as a function of their distance to the basal-plane surface layer using density-functional theory calculations. The results for HCl display large dispersions in the binding-energy results due to the appearance of distinct dissociation states. The layer-averaged results suggest that the uptake of HCl is most favorable in the two layers just below the surface, which is consistent with available experimental indications. The behavior of HF is found to be manifestly different due to the fact that it is a weaker acid. The dispersion in the binding-energy values is significantly less compared to the case of HCl, and the average values are essentially equal to the bulk value, regardless of layer position. This suggests that, in contrast to the case of HCl, there should not be any tendency for accumulation of HF near the surface.

RESUMEN

We use molecular simulation to analyze liquid dynamics in the vicinity of the liquid-liquid phase transition (LLPT) recently discovered in the modified embedded-atom model for elemental gallium. For this purpose we analyze the diffusive behavior in terms of the mean-squared displacement and self-intermediate scattering functions for two systems obtained by cooling the stable liquid through the LLPT at different cooling rates. The results show a pronounced heterogeneity of the dynamics upon the onset of the LLPT. Furthermore, it is found that this heterogeneity is closely correlated to the structural properties of the 9-fold coordinated high-density and 8-fold coordinated low-density liquid forms involved in the transition, showing a mixture of domains with very different diffusion time scales. The dynamics of the low-density liquid is found to be much more sluggish than that of the high-density form. Analysis of the energetics suggests that the origin of this difference is rooted in the fact that the cohesion in the former is significantly stronger than that in the latter.