Molecular Dynamics Simulations of Dendritic Polyelectrolytes with Flexible Spacers in Salt Free Solution

Abstract

We present the results of molecular dynamics simulations of dendritic polyelectrolytes in dilute salt-free solutions. The dendritic polyelectrolytes are modeled as an ensemble of regular-branched bead-spring chains of neutral and charged Lennard-Jones particles with explicit counterions. A wide range of molecular variables of the dendritic polyelectrolytes such as generation number, spacer length, and charge density were considered in the simulations. The effect of dendrimer size on relaxation time, the conformation of spacers, and the size dependence of the dendrimer on molecular variables are discussed and compared with a Flory type theory. The osmotic coefficients of the dilute dendritic polyelectrolyte solutions, as well as the profiles of monomers and counterions, are calculated directly from the simulations. Our simulation results show that the inner spacers of the dendrimers are extensively stretched, and the size dependence on the molecular weight deviates from the scaling prediction that assumes a Gaussian elasticity of the spacer.