Surface energy and surface stress on vicinals by revisiting the Shuttleworth relation

Hecquet, Pascal

doi:10.1016/j.susc.2017.12.014

Cited by 7 publications

(2 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For each system we then proceed to calculate γ eii . This procedure is similar to the one reported in the literature by different authors [46,78,87], who, however, consider only the case at zero temperature. In this work we will report also results for finite temperature calculations.…”

Section: B Computational Detailssupporting

confidence: 63%

A unified description of Surface Free Energy and Surface Stress

Di Pasquale,

Davidchack

2019

Preprint

View full text Add to dashboard Cite

Even though the study of interfacial phenomena dates back to Laplace and was formalised by Gibbs for liquid-liquid interfaces, it appears that some concepts and relations among them are still causing some confusion and debates in the literature. Moreover, ever since the Molecular Dynamics (MD) simulations have started to be widely used in the study of surface properties, these debates only intensified. In this work, we present a systematic description of the interfacial properties from the thermodynamic and statistical mechanics points of view. In particular, we link our derivations to MD simulations, describing precisely what different quantities represent and how they can be calculated.We do not follow the usual way that consists of describing the thermodynamics of the surfaces in general and then considering specific cases (e.g. liquid-liquid interface, liquid-solid interface).Instead, we present our analysis of various properties of surfaces in a hierarchical way, starting with the simplest case that we have identified: a single component liquid-vacuum interface, and then adding more and more complications when we progress to more complex interfaces involving solids. We propose that the term "surface tension" should not be used in the description of surfaces and interfaces involving solids, since its meaning is ambiguous. Only "Surface Free Energy" and "Surface Stress" are well defined and represent distinct, but related, properties of the interfaces. We demonstrate that these quantities, as defined in thermodynamics and measured in MD simulations, satisfy the Shuttleworth equation.

show abstract

Section: B Computational Detailssupporting

confidence: 63%

A unified description of Surface Free Energy and Surface Stress

Di Pasquale,

Davidchack

2019

Preprint

View full text Add to dashboard Cite

show abstract

“…Additionally, since the mixture interface interpolates a liquid on one side and a crystal on the other, the elastic deformation of the solid surface might influence the interfacial tension via the addition of a reversible work per interfacial area to elastically stretch the surface. This work represents the surface energy change with strain, and it must be included in all the stress-sensitive interfaces, particularly the crystal or solid surfaces, so that the interfacial tension and free energy of the liquid–crystal mixtures are different. − We generalize the formula of the interfacial tension to incorporate the elastic deformation energy using the Shuttleworth equation. − In particular, we demonstrate the need and importance of this elastic correction to the interfacial tension in the field of gas hydrates.…”

Section: Introductionmentioning

confidence: 99%

Multiscale Modeling and Simulation of Water and Methane Hydrate Crystal Interface

Mirzaeifard

Servio

Rey

2019

Crystal Growth & Design

View full text Add to dashboard Cite

Water–methane hydrate interfaces are ubiquitous in oil and gas technologies and in Nature. The structure and properties of this liquid/crystal interface plays a significant role in transport phenomena between the bulk phases. In this paper, we use molecular dynamics techniques to characterize the liquid water–crystalline methane hydrate in the bulk and, particularly, the interface. We show that the interfacial mechanical approach based on the novel constant normal pressure-cross-sectional area (NPNAT) ensemble with a computational slab length equal to the lattice parameter of the methane clathrates can accurately predict the interfacial free energy of a curved interface. Notably, the computational platform for the interfacial tension characterization includes contributions from elastic strains. In the studied temperature and pressure ranges, we find that the interfacial tension slightly increases with temperature upturn or pressure drop due to less disordered orientation and dispersed distribution of the molecules at the interface. We generate a full molecular-level characterization by computing the excess enthalpy and stress, local density profile, radial distribution function, hydrogen bonding density, and charge distribution to confirm the observed interfacial tension trend, which significantly contributes to the evolving understanding of gas hydrate formation.

show abstract