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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.

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.

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.

Using molecular dynamics simulations, we assess the uniaxial deformation response of ice Ih 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 [01̄10] 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 Ih 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 Ih. Fil: Santos Flórez, Pedro Antonio. Universidade Estadual de Campinas; Brasil Fil: Ruestes, Carlos Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza; Argentina. Universidad Nacional de Cuyo. Facultad de Ciencias Exactas y Naturales; Argentina Fil: de Koning, Maurice. Universidade Estadual de Campinas; Brasil

We present a dynamic implementation of the Clausius–Clapeyron integration (CCI) method for mapping out phase-coexistence boundaries through a single atomistic simulation run. In contrast to previous implementations, where the reversible path of coexistence conditions is generated from a series of independent equilibrium simulations, dynamic Clausius–Clapeyron integration (d-CCI) explores an entire coexistence boundary in a single nonequilibrium simulation. The method gives accurately the melting curve for a system of particles interacting through the Lennard-Jones potential. Furthermore, we apply d-CCI to compute the melting curve of an ab initio pair potential for argon and verify earlier studies on the effects of many-body interactions and quantum effects in the melting of argon. The d-CCI method shows to be effective in both applications, giving converged coexistence curves spanning a wide range of thermodynamic states from relatively short nonequilibrium simulations.

Agradecimentos: We gratefully acknowledge support from the Brazilian agencies CNPq, Fapesp, and Capes. Part of the calculations were performed at CCJDR-IFGW-UNICAMP and CENAPAD-SP Abstract: 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 CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQ FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESP COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPES Fechado

We develop a general theoretical framework for the recently proposed importance sampling method for enhancing the efficiency of rare-event simulations [W. Cai, M. H. Kalos, M. de Koning, and V. V. Bulatov, Phys. Rev. E 66, 046703 (2002)], and discuss practical aspects of its application. We define the success/fail ensemble of all possible successful and failed transition paths of any duration and demonstrate that in this formulation the rare-event problem can be interpreted as a "hit-or-miss" Monte Carlo quadrature calculation of a path integral. The fact that the integrand contributes significantly only for a very tiny fraction of all possible paths then naturally leads to a "standard" importance sampling approach to Monte Carlo (MC) quadrature and the existence of an optimal importance function. In addition to showing that the approach is general and expected to be applicable beyond the realm of Markovian path simulations, for which the method was originally proposed, the formulation reveals a conceptual analogy with the variational MC (VMC) method. The search for the optimal importance function in the former is analogous to finding the ground-state wave function in the latter. In two model problems we discuss practical aspects of finding a suitable approximation for the optimal importance function. For this purpose we follow the strategy that is typically adopted in VMC calculations: the selection of a trial functional form for the optimal importance function, followed by the optimization of its adjustable parameters. The latter is accomplished by means of an adaptive optimization procedure based on a combination of steepest-descent and genetic algorithms.