Contributions of Far-Field Hydrodynamic Interactions to the Kinetics of Electrostatically Driven Molecular Association

Abstract

We simulated the diffusional encounters in periodic systems of model isotropic and anisotropic molecules using Brownian dynamics. We considered the electrostatic, excluded volume, and far-field hydrodynamic forces between diffusing molecules. Our goal was to estimate to what extent the hydrodynamic interactions influence the association kinetics when the associating partners are oppositely charged and their direct electrostatic interactions are screened by small mobile ions of dissolved salt. Overall, including hydrodynamic interactions decreases the association rate constants. The relative magnitude of this decrease does not depend on the ionic strength for the association of isotropic charged objects. This also holds true for nonspecific association (i.e., without restrictions regarding the relative orientation of binding partners in an encounter complex) of anisotropic objects. However, such dependence is visible for orientation-specific association of anisotropic objects. Moreover, we observe that some orientations of anisotropic molecules are hydrodynamically favorable during their mutual approach, and that such molecules can be hydrodynamically steered toward a particular relative orientation. This hydrodynamic orientational steering is impeded in case of strong electrostatic interactions or steric hindrance.