The assembly of two non-polar nanoscopic bodies is studied within the framework of Brownian dynamics. The potential of mean force and hydrodynamic interactions are computed from molecular dynamics simulations in explicit solvent. We find that molecular scale effects dominate at short distances, thus giving rise to deviations from the predictions of continuum hydrodynamic theory. Distinct signatures of the molecular scale are engendered by drying phenomena and solvent layering and fluctuations. The rate of assembly in the diffusion controlled limit is found to decrease when molecular scale hydrodynamic interactions are included. Such effects are in opposition to the free energy driving force of ideal hydrophobic assembly, whereas they act in concert in the assembly of more hydrophilic bodies.

Interplay between hydrodynamics and the free energy surface in the assembly of nanoscale hydrophobes

243rd National Meeting (2012)

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