title: A comparison of implicit- and explicit-solvent simulations of self-assembly in block copolymer and solute systems.
abstract: We have developed explicit- and implicit-solvent models for the flash nanoprecipitation process, which involves rapid coprecipitation of block copolymers and solutes by changing solvent quality. The explicit-solvent model uses the dissipative particle dynamics (DPD) method and the implicit-solvent model uses the Brownian dynamics (BD) method. Each of the two models was parameterized to match key properties of the diblock copolymer (specifically, critical micelle concentration, diffusion coefficient, polystyrene melt density, and polyethylene glycol radius of gyration) and the hydrophobic solute (aqueous solubility, diffusion coefficient, and solid density). The models were simulated in the limit of instantaneous mixing of solvent with antisolvent. Despite the significant differences in the potentials employed in the implicit- and explicit-solvent models, the polymer-stabilized nanoparticles formed in both sets of simulations are similar in size and structure; however, the dynamic evolution of the two simulations is quite different. Nanoparticles in the BD simulations have diffusion coefficients that follow Rouse behavior (D ∝ M(-1)), whereas those in the DPD simulations have diffusion coefficients that are close to the values predicted by the Stokes-Einstein relation (D ∝ R(-1)). As the nanoparticles become larger, the discrepancy between diffusion coefficients grows. As a consequence, BD simulations produce increasingly slower aggregation dynamics with respect to real time and result in an unphysical evolution of the nanoparticle size distribution. Surface area per polymer of the stable explicit-solvent nanoparticles agrees well with experimental values, whereas the implicit-solvent nanoparticles are stable when the surface area per particle is roughly two to four times larger. We conclude that implicit-solvent models may produce questionable results when simulating nonequilibrium processes in which hydrodynamics play a critical role.
authors.affiliation: Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544-5263, USA. jspaeth@princeton.edu
authors.forename: Justin R
authors.initials: JR
authors.lastname: Spaeth
authors.forename: Ioannis G
authors.initials: IG
authors.lastname: Kevrekidis
authors.forename: Athanassios Z
authors.initials: AZ
authors.lastname: Panagiotopoulos
mesh_terms: D003198:Computer Simulation; D057446:Hydrodynamics; D008956:Models, Chemical; D053758:Nanoparticles / Q000737:chemistry; D011108:Polymers / Q000737:chemistry*; D012996:Solutions; D012997:Solvents / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D011108:Polymers; D012996:Solutions; D012997:Solvents; D014867:Water