Efficient Modeling of High-Generation Dendrimers in Solution Using Dynamical Self-Consistent Field Theory

We extend dynamical self-consistent field theory (dSCFT) to large, nonlinear polymer chains to simulate the evolution of high-generation dendrimers in a solvent. Because the number of beads N within these bead–spring dendrimers is very large, we introduce a numerical technique to efficiently analyze the Rouse modes of the dendrimer through a decomposition of the dendrimer into many smaller subchains, achieving a significant improvement, from O(N2) to O(N), in the scaling of the simulation time for the Rouse motion of the dendrimer. By adjusting the strength of the interaction between dendrimer and solvent beads, we obtain qualitative and quantitative agreement with the core-chain morphology, 22 nm radius, and high degree of hydration measured experimentally using small-angle neutron scattering for 11-generation, glucose-based phytoglycogen dendrimers in water, validating dSCFT in this context.