(34f) Unraveling Nonequilibrium Dynamics in Macromolecular Solution Phase Behavior

Understanding the emergence of mesoscale order in soft matter systems far from equilibrium remains a central challenge in molecular thermodynamics. In this work, we develop and apply a computational framework based on dynamical density functional theory (DDFT) to model the spatiotemporal evolution of clustering and phase separation in dilute macromolecular solutions. Going beyond classical nucleation theory, our approach captures the formation of long-lived, solute-rich mesoscopic clusters under conditions where bulk phase separation is thermodynamically unfavorable. We demonstrate how the interplay between molecular-scale interactions, driven diffusion, and dynamic arrest gives rise to a rich variety of nonequilibrium morphologies.

By integrating molecular-level input such as effective Flory-Huggins parameters and single-chain conformational statistics, our model bridges the gap between microscopic physics and continuum behavior. Simulations reveal how subtle shifts in concentration, solvent quality, or interaction asymmetry can tune the size, lifetime, and spatial distribution of emergent clusters. The results shed light on key mechanisms relevant to pre-nucleation phenomena in biomolecular condensates and other metastable soft matter systems.

This work opens new frontiers in predictive mesoscale modeling of dynamic self-assembly, offering a route to design principles for responsive, out-of-equilibrium materials.