Are hydrodynamic interactions important in the kinetics of hydrophobic collapse?

Abstract

We study the kinetics of assembly of two plates of varying hydrophobicity, including cases where drying occurs and water strongly solvates the plate surfaces. The potential of mean force and molecular-scale hydrodynamics are computed from molecular dynamics simulations in explicit solvent as a function of particle separation. In agreement with our recent work on nanospheres [J. Phys. Chem. B 116, 378 (2012)] regions of high friction are found to be engendered by large and slow solvent fluctuations. These slow fluctuations can be due to either drying or confinement. The mean first passage times for assembly are computed by means of molecular dynamics simulations in explicit solvent and by Brownian dynamics simulations along the reaction path. Brownian dynamics makes use of the potential of mean force and hydrodynamic profile that we determined. Surprisingly, we find reasonable agreement between full scale molecular dynamics and Brownian dynamics, despite the role of slow solvent relaxation in the assembly process. We found that molecular scale hydrodynamic interactions are essential in describing the kinetics of assembly.

6 figures, 13 pages

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• Canonical sampling through velocity-rescaling
• Nanofluidics, from bulk to interfaces
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• Evaporation Rate of Water in Hydrophobic Confinement
• The Role of Solvent Fluctuations in Hydrophobic Assembly
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• The Interfacial-Organized Monolayer Water Hindering the Aggregation of Nanographene: Both in Stacking and Sliding Assembly Pathways
• Variational implicit-solvent predictions of the dry-wet transition pathways for ligand-receptor binding and unbinding kinetics
• Affinity, Kinetics, and Pathways of Anisotropic Ligands Binding to Hydrophobic Model Pockets