Understanding Dynamics in Coarse-Grained Models: V. Extension of Coarse-Grained Dynamics Theory to Non-Hard Sphere Systems

TL;DR

This paper extends the coarse-grained dynamics theory from hard sphere systems to non-hard sphere systems using perturbation theory, enabling broader application to various liquid models in molecular simulations.

Contribution

It generalizes the existing hard sphere-based CG dynamics theory to non-hard sphere systems by incorporating excess entropy corrections via Weeks-Chandler-Andersen perturbation theory.

Findings

Successfully applied to different liquid interactions

Provides a generalized framework for Gaussian CG models

Enhances applicability of CG dynamics theory

Abstract

Coarse-grained (CG) modeling has gained significant attention in recent years due to its wide applicability in enhancing the spatiotemporal scales of molecular simulations. While CG simulations, often performed with Hamiltonian mechanics, faithfully recapitulate structural correlations at equilibrium, they lead to ambiguously accelerated dynamics. In the first paper of this series [J. Chem. Phys. 158, 034103 (2023)], we proposed the excess entropy scaling relationship to understand the CG dynamics. Then, in the following companion paper [J. Chem. Phys. 158, 034104 (2023)], we developed a theory to map the CG system into a dynamically-consistent hard sphere system to analytically derive an expression for fast CG dynamics. However, many chemical and physical systems do not exhibit hard sphere-like behavior, limiting the extensibility of the developed theory. In this paper, we aim to generalize the theory to the non-hard sphere system based on the Weeks-Chandler-Andersen perturbation theory. Since non-hard sphere-like CG interactions affect the excess entropy term as it deviates from the hard sphere description, we explicitly account for the extra entropy to correct the non-hard sphere nature of the system. This approach is demonstrated for two different types of interactions seen in liquids, and we further provide a generalized description for any CG models using the generalized Gaussian CG models using Gaussian basis sets. Altogether, this work allows for extending the range and applicability of the hard sphere CG dynamics theory to a myriad of CG liquids.