Thermodynamic relations at the coupling boundary in adaptive resolution simulations for open systems

TL;DR

This paper derives thermodynamic relations for the adaptive resolution simulation (AdResS) technique, demonstrating its validity as a method for simulating open systems by linking its chemical potential to that of fully atomistic models.

Contribution

It provides a theoretical and numerical foundation for AdResS as an open system simulation method, including explicit relations for chemical potential and grand potential.

Findings

Thermodynamic relations justify AdResS as an open system.

Chemical potential in AdResS matches that of reference atomistic systems.

Grand potential of AdResS can be explicitly expressed.

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 was 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 system, we derive thermodynamic relations for AdResS which justify conceptually and numerically the claim of AdResS as a technique for simulating open systems. In particular, we derive the relation between the chemical potential of the AdResS set-up and that of its reference fully atomistic simulation. 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.