Free Energy Cost to Assemble Superlattices of Polymer-Grafted Nanoparticles

TL;DR

This paper introduces a simulation method to quantify the free energy costs of assembling polymer-grafted nanoparticles into superlattices, revealing BCC as the most stable structure beyond mean-field explanations.

Contribution

A novel simulation approach to calculate free energy costs of PGNPs deforming into superlattice structures, providing molecular insights into stability beyond mean-field theories.

Findings

BCC is most stable among studied structures.

Free energy differences quantified between BCC, FCC, and A15.

Corona entropy is similar across different lattice types.

Abstract

Mesoparticles consisting of a hard core and a soft corona like polymer-grafted nanoparticles (PGNPs) can assemble into various superlattice structures, in which each mesoparticle assumes the shape of the corresponding Wigner-Seitz (or Voronoi) cell. Conventional wisdom often perceives the stability of these superlattices in a mean-field view of surface area minimization or corona entropy maximization, which lacks a molecular interpretation. We develop a simulation method to calculate the free energy cost to deform spherical PGNPs into Wigner-Seitz polyhedra, which are then relaxed in a certain crystalline superlattice. With this method, we successfully quantify the free energy differences between model BCC, FCC and A15 systems of PGNPs and identify BCC as the most stable structure in most cases. Analysis of polymer configurations in the corona, whose boundary is blurred by chain interpenetration, shows that the radial distribution of grafted chains and the corresponding entropy is almost identical among BCC and FCC, suggesting that the higher stability of BCC structure cannot be explained by a mean-field description of corona shape.