A unified description of Surface Free Energy and Surface Stress

TL;DR

This paper clarifies the concepts of Surface Free Energy and Surface Stress, linking thermodynamics and MD simulations, and proposes avoiding the ambiguous term 'surface tension' for solid interfaces.

Contribution

It provides a hierarchical, systematic analysis of interfacial properties, emphasizing clear definitions and their relation to MD simulations, especially for solid interfaces.

Findings

Surface Free Energy and Surface Stress are distinct but related properties.

The Shuttleworth equation is satisfied by these quantities in MD simulations.

The term 'surface tension' should be avoided for solid interfaces.

Abstract

Even though the study of interfacial phenomena dates back to Laplace and was formalised by Gibbs, it appears that some concepts and relations among them are still causing some confusion and debates in the literature, particularly for interfaces involving solids. 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.