Reframing the coupling force of adaptive resolution simulation in terms of the Liouville-type hierarchy for open systems

Abstract

In this work, we present a novel perspective on the coupling force employed to compensate the interface artifacts prevalent in adaptive resolution simulations (AdResS) of open many-particle systems. We show that a substantial part of this "thermodynamic force" can be framed in terms of the theoretical model of the Liouville-type hierarchy for open systems. The correspondence is made explicit for the case of a simple atomistic fluid, for which a one-dimensional integral expression is derived. This enables the analysis for dependencies of the thermodynamic force on important simulation parameters, which is taken to inspire both simplifications for the numerical calculation of the thermodynamic force and new criteria for its validation that are adequate to the interfacial nature of the problem. The theoretical claims are then verified in a simulation study of the atomistic supercritical Lennard-Jones fluid at different thermodynamic states.