Uniaxial-deformation behavior of ice Ih as described by the TIP4P/Ice and mW water models

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; BrasilFil: 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; ArgentinaFil: de Koning, Maurice. Universidade Estadual de Campinas; Brasi

Nonequilibrium Processes in Repulsive Binary Mixtures

We consider rapid cooling processes in classical, 3-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

Determinação de energias livres através do método de ligação adiabática usando dinâmica molecular

Orientador: Alex AntonelliTese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb WataghinResumo: A determinação de quantidades térmicas (energia livre, entropia) usando o método de ligação adiabática através de dinâmica molecular {DM) é investigada. A base teórica do método está enraizada nas expressões termodinâmicas macroscópicas da termodinâmica de processos reversíveis. A técnica de DM, utilizando conjuntos adequados de equações clássicas de movimento, pode ser usada para a simulação de tais processos sob diversas condições. Devido ao tempo limitado de computação, os processos gerados pela DM são sujeitos à dissipação de energia causando erros na determinação das quantidades térmicas. Desenvolvemos procedimentos para a correção simples e rápida destes erros. O desempenho do método é investigado em várias aplicações envolvendo sistemas e processos físicos com características diferentes. O método é aplicado ao cálculo da diferença de energia livre de Helmholtz entre dois cristais harmônicos {Einstein) com freqüências diferentes. Em seguida, o método é utilizado para o cobre com o objetivo de calcular a energia livre do cristal perfeito e a energia livre de formação de uma vacância em função da temperatura. Finalmente, aplicamos o método para estudar os aspectos energéticos relacionados ao papel da nucleação de deslocações em planos de deslizamento {111} do silício na transição brittle-ductile. A avaliação do desempenho do método de ligação adiabática através de dinâmica molecular mostra que este método é uma ferramenta muito flexível e poderosa na determinação, de maneira eficiente e quantitativamente confiável, de quantidades térmicas em uma grande variedade de sistemas e processos físicosAbstract: The determination of thermal quantities (free energy, entropy) using the molecular dynamics (MD) adiabatic switching method is investigated. The theoretical basis of the method is rooted in the macroscopic thermodynamic relations of reversible processes, and the MD technique, using suitable sets of classical equations of motion, can be used for the simulation of such processes under several conditions. Due to the limited computer time, the processes generated by MD are subject to energy dissipation, causing errors in the determination of thermal quantities. We develop procedures for the simple and fast correction of these errors. The performance of the method is investigated in various applications involving several physical systems and processes with different characteristics. The method is applied to the calculation of thc Helmholtz free energy difference between harmonic (Einstein) crystals with different frequencies, after which it is utilized to calculate the bulk, and vacancy formation free energies in copper as a function of temperature. Finally, the method is applied to study energetic aspects related to the role of dislocation nucleation on {111} slip planes in the brittle-ductile transition in silicon. The evaluation of the performance of the MD adiabatic switching method shows that it is a very flexible and powerful tool for the quantitatively reliable and efficient determination of thermal quantities in a wide variety of physical systems and processesDoutoradoFísicaDoutor em Ciência

First-principles prediction of a metastable crystalline phase of Ga with Cmcm symmetry

FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORWe report on evidence for the existence of an unknown metastable crystalline phase of gallium by the combination of classical molecular-dynamics (MD) simulations and density-functional theory (DFT) calculations. The MD simulations, based on a modified embedded-atom potential, reveal the unknown crystalline form through a first-order phase transition originating from the Cmca symmetric ?-Ga phase under hydrostatic tension. Subsequently, the DFT calculations using two different generalized-gradient approximation functionals are employed to verify its stability and determine its electronic structure. The structure of the orthorhombic phase is described by symmetry group Cmcm and shows a dimer arrangement resembling the ?-Ga phase. A first-order phase transition from ?-Ga to the unknown phase is estimated to occur at ?1.3 GPa.We report on evidence for the existence of an unknown metastable crystalline phase of gallium by the combination of classical molecular-dynamics (MD) simulations and density-functional theory (DFT) calculations. The MD simulations, based on a modified embedded-atom potential, reveal the unknown crystalline form through a first-order phase transition originating from the Cmca symmetric α-Ga phase under hydrostatic tension. Subsequently, the DFT calculations using two different generalized-gradient approximation functionals are employed to verify its stability and determine its electronic structure. The structure of the orthorhombic phase is described by symmetry group Cmcm and shows a dimer arrangement resembling the α-Ga phase. A first-order phase transition from α-Ga to the unknown phase is estimated to occur at −1.3 GPa.80414FAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORSem informaçãoSem informaçãoSem informaçãoThe work was supported by the Brazilian agencies FAPESP, CNPq, and CAPES. Part of the computations was carried out at CENAPAD-SP

Dislocation structure and mobility in hcp He-4

CNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORUsing path-integral Monte Carlo simulations, we assess the core structure and mobility of the screw and edge basal-plane dislocations in hcp He-4. Our findings provide key insights into recent interpretations of giant plasticity and mass flow junction experiments. First, both dislocations are dissociated into nonsuperfluid Shockley partial dislocations separated by ribbons of stacking fault, suggesting that they are unlikely to act as one-dimensional channels that may display Luttinger-liquid-like behavior. Second, the centroid positions of the partial cores are found to fluctuate substantially, even in the absence of applied shear stresses. This implies that the lattice resistance to motion of the partial dislocations is negligible, consistent with the recent experimental observations of giant plasticity. Further results indicate that both the structure of the partial cores and the zero-point fluctuations play a role in this extreme mobility.Using path-integral Monte Carlo simulations, we assess the core structure and mobility of the screw and edge basal-plane dislocations in hcp He-4. Our findings provide key insights into recent interpretations of giant plasticity and mass flow junction experiments. First, both dislocations are dissociated into nonsuperfluid Shockley partial dislocations separated by ribbons of stacking fault, suggesting that they are unlikely to act as one-dimensional channels that may display Luttinger-liquid-like behavior. Second, the centroid positions of the partial cores are found to fluctuate substantially, even in the absence of applied shear stresses. This implies that the lattice resistance to motion of the partial dislocations is negligible, consistent with the recent experimental observations of giant plasticity. Further results indicate that both the structure of the partial cores and the zero-point fluctuations play a role in this extreme mobility.117415CNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORCNPQ - CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICOFAPESP - FUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULOCAPES - COORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIORSem informação2013/08293-7Sem informaçãoE. J. L. B. and M. K. gratefully acknowledge support from the Brazilian agencies CNPq, Fapesp, and Capes. M. K. acknowledges support from the Center for Computational Engineering and Sciences, Fapesp/Cepid Grant No. 2013/08293-7. This work was partially supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award No. DE-SC0010412 (W. C.). This work was supported in part by the U.S. Department of Energy at the Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344

Atomistic Simulation of Nanoindentation of Ice Ih

Using molecular dynamics simulations, we study the nanoindentation response of the ice Ih basal surface using two popular water models, namely, the all-atom TIP4P/Ice potential and the coarse-grained mW model. In particular, we consider two markedly different temperatures at which a quasi-liquid layer (QLL) is or is not present. We discuss loading curves, hardness estimates, deformation mechanisms, and residual imprints, considering the effect of the QLL, indenter size, and penetration rate. At very low temperatures, in the absence of a QLL, both potentials produce similar loading curves and deformation mechanisms. Close to the melting temperature, however, important differences were found, including deviations in the QLL thickness and fraction as well as the presence of a competition between pressure-induced melting and recrystallization events. Nevertheless, both potentials exhibit similar deformation mechanisms and steady-state hardness estimates that are consistent with experimental data. In addition to contributing to the discussion regarding the interpretation of experimental AFM loading curves, the present results provide valuable information concerning the simulation of contact problems involving ice and the behavior of these two popular water models under such circumstances.Fil: Santos Flórez, Pedro Antonio. Universidade Estadual de Campinas; BrasilFil: Ruestes, Carlos Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Interdisciplinario de Ciencias Básicas. - Universidad Nacional de Cuyo. Instituto Interdisciplinario de Ciencias Básicas; ArgentinaFil: De Koning, Maurice. Universidade Estadual de Campinas; Brasi

On The Nature Of The Solvated Electron In Ice Ih.

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.184652-465