Abstract
We investigate polyelectrolyte stars having a moderate number of arms by molecular dynamics simulations of a coarse-grained model over a range of polyelectrolyte concentrations, where both the counter-ions and solvent are treated explicitly. This class of polymeric materials is found to exhibit rather distinct static and dynamic properties from linear and highly branched star polyelectrolyte solutions emphasized in past studies. Moderately branched polymers are particle-like in many of their properties, while at the same time they exhibit large fluctuations in size and shape as in the case of linear chain polymers. Correspondingly, these fluctuations suppress crystallization at high polymer concentrations, leading apparently to an amorphous rather than crystalline solid state at high polyelectrolyte concentrations. We quantify the onset of this transition by measuring the polymer size and shape fluctuations of our model star polyelectrolytes and the static and dynamic structure factor of these solutions over a wide range of polyelectrolyte concentration. Our findings for star polyelectrolytes are similar to those of polymer-grafted nanoparticles having a moderate grafting density, which is natural given the soft and highly deformable nature of both of these "particles."