Free energy cost to assemble superlattices of polymer-grafted nanoparticles

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 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 are almost identical between BCC and FCC, suggesting that the higher stability of the BCC structure cannot be explained by the mean-field description of the corona shape.