Coarse-Grained Molecular Dynamics Simulations of Depletion-Induced Interactions for Soft Matter Systems

TL;DR

This study compares two coarse-grained MD models for depletion interactions in soft matter, showing that the softer combinatorial-WCA model captures deeper depletion wells and aligns well with Morphometric Thermodynamics predictions.

Contribution

It introduces and evaluates the effectiveness of shifted- and combinatorial-WCA potentials in modeling depletion effects in soft matter systems, highlighting the advantages of the softer model.

Findings

Combinatorial-WCA yields deeper depletion wells than shifted-WCA.

Both models' pair potentials align with Morphometric Thermodynamics.

Combinatorial-WCA is more efficient at lower depletant densities.

Abstract

Given the ubiquity of depletion effects in biological and other soft matter systems, it is desirable to have coarse-grained Molecular Dynamics simulation approaches appropriate for the study of complex systems. This paper examines the use of two common truncated Lennard-Jones (WCA) potentials to describe a pair of colloidal particles in a thermal bath of depletants. The shifted-WCA model is the steeper of the two repulsive potentials considered, while the combinatorial-WCA model is the softer. It is found that the depletion-induced well depth for the combinatorial-WCA model is significantly deeper than the shifted-WCA model because the resulting overlap of the colloids yields extra accessible volume for depletants. For both shifted- and combinatorial-WCA simulations, the second virial coefficients and pair potentials between colloids are demonstrated to be well approximated by the Morphometric Thermodynamics (MT) model. This agreement suggests that the presence of depletants can be accurately modelled in MD simulations by implicitly including them through simple, analytical MT forms for depletion-induced interactions. Although both WCA potentials are found to be effective generic coarse-grained simulation approaches for studying depletion effects in complicated soft matter systems, combinatorial-WCA is the more efficient approach as depletion effects are enhanced at lower depletant densities. The findings indicate that for soft matter systems that are better modelled by potentials with some compressibility, predictions from hard-sphere systems could greatly underestimate the magnitude of depletion effects at a given depletant density.