A unified interpretation of stress in molecular systems (Q5962114)

The authors focus their attention on a particular aspect of continuum-atomistic connection, namely on the interpretation of the (Cauchy) stress tensor in a discrete system. This question has been explored from many different perspectives for nearly two hundred years, and this has led to various definitions that do not appear to be consistent with each other. In particular, the ``correct'' definition of the stress tensor has been a subject of great debate and controversy. In this paper, the authors establish a unified framework based on the Irving-Kirkwood-Noll procedure, which leads to all of the main stress definitions and identities, as well as to possible additional definitions. Since all of the definitions are obtained from a common framework, the authors are able to explore the connections between them and to prove the uniqueness of the stress tensor. The work starts with a derivation of the virial stress tensor using the equilibrium statistical mechanics and the technique of canonical transformations. The authors extend the Irving-Kirkwood-Noll procedure, originally derived for pair-potential interactions, to multi-body potentials. Due to the invariance of the potential energy function with respect to the Euclidean group, the multi-body potential can be expressed as a function of distances between particles. The macroscopic stress tensor corresponding to the pointwise stress tensor is obtained through a procedure of spatial averaging. A connection between this stress and stress tensors obtained via the direct spatial averaging Murdoch-Hardy procedure is explored, and the latter procedure is generalized to multi-body potentials. The existence of different extensions for the potential energy function leads to non-uniqueness of the pointwise stress tensor, and also results in the non-uniqueness of the above definitions. However, it is shown that the difference in the macroscopic stress tensor resulting from this non-uniqueness tends to zero in the thermodynamic limit. For practical aspects, these different definitions obtained within the unified framework, are investigated using several ``numerical experiments'' involving molecular dynamics and lattice statics. These simulations are performed to examine the behavior of these stress definitions, including their convergence with averaging the domain size, and their symmetry properties.