Accurate structure-based coarse-graining leads to consistent barrier-crossing dynamics

TL;DR

This paper introduces a multisurface dynamics approach for structure-based coarse-graining in molecular systems, enabling more accurate and consistent long-time barrier-crossing dynamics by coupling multiple conformational basins.

Contribution

It extends multisurface dynamics to classical systems, improving the sampling of conformational ensembles and long-time dynamics in coarse-grained models.

Findings

Achieves consistent barrier-crossing dynamics in coarse-grained models.

Systematically improves conformational sampling with more surfaces.

Enhances long-time accuracy of molecular simulations.

Abstract

Structure-based coarse graining of molecular systems offers a systematic route to reproduce the many-body potential of mean force. Unfortunately, common strategies are inherently limited by the molecular mechanics force field employed. Here, we extend the concept of multisurface dynamics, initially developed to describe electronic transitions in chemical reactions, to accurately sample the conformational ensemble of a classical system in equilibrium. In analogy to describing different electronic configurations, a surface-hopping scheme couples distinct conformational basins beyond the additivity of the Hamiltonian. The incorporation of more surfaces leads systematically toward improved cross-correlations. The resulting models naturally achieve consistent long-time dynamics for systems governed by barrier-crossing events.