Tethered polyelectrolytes under the action of an electrical field: a molecular-dynamics study.

For a polyelectrolyte undergoing electrophoretic motion, it is predicted (D. Long, J.L. Viovy, A. Ajdari, Phys. Rev. Lett. 76, 3858 (1996); D. Long, A. Ajdari, Electrophoresis 17, 1161 (1996)) that the mechanical force necessary to stall the molecule is substantially smaller than the sum of electrical forces applied on all monomers. In fact, it should be proportional to its hydrodynamic friction coefficient and therefore to the size of its conformation. In our work we examine this prediction using coarse-grained molecular-dynamics simulations in which we explicitly include the polymer, the solvent, the counterions and salt. The electrophoretic mobility of polyelectrolytes is evaluated, the mechanical force necessary to keep the molecules tethered is measured and the resulting anisotropic polymer conformations are observed and quantified. Our results corroborate Long et al.'s prediction.