Understanding Dynamics in Coarse-Grained Models: V. Extension of Coarse-Grained Dynamics Theory to Non-Hard Sphere Systems
arXiv:2412.17186 · doi:10.1063/5.0254388
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.
47 pages, 13 figures
References in corpus (32)
- Testing Mode-Coupling Theory for a Supercooled Binary Lennard-Jones Mixture I: The van Hove Correlation Function
- Pressure-energy correlations in liquids. IV. "Isomorphs" in liquid state diagrams
- "Isomorphs" in liquid state diagrams
- Mean Field Fluid Behavior of the Gaussian Core Model
- In Search of Colloidal Hard Spheres
- Fluid and solid phases of the Gaussian core model
- Elastically Cooperative Activated Barrier Hopping Theory of Relaxation in Viscous Fluids. I. General Formulation and Application to Hard Sphere Fluids
- Elastically Cooperative Activated Barrier Hopping Theory of Relaxation in Viscous Fluids. II. Thermal Liquids
- Phase diagram of the Gaussian-core model
- Water-like hierarchy of anomalies in a continuous spherical shouldered potential
- Growing point-to-set length scale correlates with growing relaxation times in model supercooled liquids
- Liquid-Liquid Phase Transitions for Soft-Core Attractive Potentials
- Unified Theory of Activated Relaxation in Liquids over 14 Decades in Time
- Pressure-energy correlations in liquids. V. Isomorphs in generalized Lennard-Jones systems
- A repulsive reference potential reproducing the dynamics of a liquid with attractions
- Resolving Dynamic Properties of Polymers through Coarse-Grained Computational Studies
- Relationship between Entropy and Diffusion: A statistical mechanical derivation of Rosenfeld expression for a rugged energy landscape
- Understanding Dynamics in Coarse-Grained Models: I. Universal Excess Entropy Scaling Relationship
- Hard sphere-like dynamics in a non hard sphere liquid
- Unraveling the success and failure of mode coupling theory from consideration of entropy
- Universal correlations between the fragility and interparticle repulsion of glass-forming liquids
- Understanding Dynamics in Coarse-Grained Models: II. Coarse-Grained Diffusion Modeled Using Hard Sphere Theory
- Density functional theory of inhomogeneous liquids. I. The liquid-vapor interface in Lennard-Jones fluids
- Anomalous dimensionality dependence of diffusion in a rugged energy landscape : How pathological is one dimension ?
- Comparing four hard-sphere approximations for the low-temperature WCA melting line
- Relative Resolution: A Computationally Efficient Implementation in LAMMPS
- Universal Relation between Entropy and Kinetics
- Entropy of different phases formed by soft rods
- Understanding Dynamics in Coarse-Grained Models: IV. Connection of Fine-Grained and Coarse-Grained Dynamics with the Stokes-Einstein and Stokes-Einstein-Debye Relations
- Relative Resolution: An Analysis with the Kullback-Leibler Entropy
- Relative Resolution: A Multipole Approximation at Appropriate Distances
- Hierarchical Framework for Predicting Entropies in Bottom-Up Coarse-Grained Models