Stress and heat flux for arbitrary multi-body potentials: A unified framework

TL;DR

This paper introduces a comprehensive framework to evaluate continuum fields like stress and heat flux from molecular simulations involving arbitrary multi-body potentials, addressing ambiguities in force and energy decomposition.

Contribution

It generalizes the Irving-Kirkwood procedure to multi-body potentials and resolves key ambiguities, providing more physically consistent expressions for internal energy and heat flux.

Findings

New expressions for internal energy and heat flux are more physically reasonable.

The framework recovers standard microscopic definitions as special cases.

Numerical experiments validate the new energy expression.

Abstract

A two-step unified framework for the evaluation of continuum field expressions from molecular simulations for arbitrary interatomic potentials is presented. First, pointwise continuum fields are obtained using a generalization of the Irving-Kirkwood procedure to arbitrary multi-body potentials. Two ambiguities associated with the original Irving-Kirkwood procedure (which was limited to pair potential interactions) are addressed in its generalization. The first ambiguity is due to the non-uniqueness of the decomposition of the force on an atom as a sum of central forces, which is a result of the non-uniqueness of the potential energy representation in terms of distances between the particles. This is in turn related to the shape space of the system. The second ambiguity is due to the non-uniqueness of the energy decomposition between particles. The latter can be completely avoided through an alternate derivation for the energy balance. It is found that the expressions for the specific internal energy and the heat flux obtained through the alternate derivation are quite different from the original Irving-Kirkwood procedure and appear to be more physically reasonable. Next, in the second step of the unified framework, spatial averaging is applied to the pointwise field to obtain the corresponding macroscopic quantities. These lead to expressions suitable for computation in molecular dynamics simulations. It is shown that the important commonly-used microscopic definitions for the stress tensor and heat flux vector are recovered in this process as special cases (generalized to arbitrary multi-body potentials). Several numerical experiments are conducted to compare the new expression for the specific internal energy with the original one.