Simulation of polyelectrolyte electrophoresis: effects of the aspect ratio, double-layer polarization, effective charge, and electroosmotic flow.

The electrophoresis of a deformable polyelectrolyte (PE) is studied theoretically by considering a Poisson-Nernst-Planck model coupled with modified Navier-Stokes equations, taking account of the effects of double-layer polarization, counterion condensation, and electroosmotic flow. The influences of the local electric field and the effective PE charge on the PE mobility are discussed, thereby providing a complete picture for the phenomenon under consideration. Our model explains successfully the presence of a local minimum in the mobility of a highly charged PE as the bulk salt concentration varies, as observed experimentally. Numerical simulation also reveals several interesting and important results. For example, the more a PE is stretched in the direction of electrophoresis, the larger is its mobility. As the double layer becomes thin, the local electric field becomes independent of the PE shape, and its behavior mainly depends upon its effective charge. We show that the force that stretches a PE is maximal when it is spherical and decreases with an increasing aspect ratio, which has not been reported previously.