Thermodynamic Relations at the Coupling Boundary in Adaptive Resolution Simulations for Open Systems

Abstract

The adaptive resolution simulation (AdResS) technique couples regions with different molecular resolutions and allows the exchange of molecules between different regions in an adaptive fashion. The latest development of the technique allows to abruptly couple the atomistically resolved region with a region of non‐interacting point‐like particles. The abrupt set‐up is derived having in mind the idea of the atomistically resolved region as an open system embedded in a large reservoir at a given macroscopic state. In this work, starting from the idea of open systems, the authors derive thermodynamic relations for AdResS which justify conceptually and numerically the claim of AdResS as a technique for simulating open systems. In particular, the relation between the chemical potential of the AdResS set‐up and that of its reference fully atomistic simulation is derived. The implication of this result is that the grand potential of AdResS can be explicitly written and thus, from a statistical mechanics point of view, the atomistically resolved region of AdResS can be identified with a well‐defined open system.