Effect of counterion excluded volume on the conformational behavior of polyelectrolyte chains

Conformational behavior of a single strongly charged polyelectrolyte chain in a dilute solution is studied by molecular dynamics simulations. The novel feature of the model is variation of the excluded volume of counterions for investigating its effect on the chain conformation, especially in low-polar media. It has been confirmed that the chain with conventional counterions collapses into a dense globule with increasing electrostatic interactions. However, if the counterions are bulky enough, they prevent the chain collapse even in media with strong electrostatic interactions. They stay bound in the vicinity of the backbone of the chain that adopts a swollen conformation. In this conformation, the scaling relation for the polymer dimensions with the chain length is the same as for neutral macromolecules in a good solvent, however the polyelectrolyte chain complexed with bulky counterions has a larger gyration radius than its uncharged analogue due to the excluded volume of the counterions contributing to the chain rigidity. Study of the counterion mobility has shown that, similar to the conventional counterions, the bulky counterions do not form stable ion pairs with ions on the polymer chain even in media with strong electrostatic interactions, but rather freely move along the chain backbone. In solutions containing mixtures of counterions with a bimodal size distribution, the conformations of linear polyelectrolytes depend considerably on the fraction of bulky counterions. Furthermore, a kind of intramolecular microphase separation can take place within a polyelectrolyte globule with the formation of a core–shell particle: the smaller counterions concentrate within the globular core while the bulkier counterions form a shell on the globule surface. The stability of the core–shell globule depends on the relative size of the counterions as well as their fractions in the solution. Thus, fine tuning of the balance between the counterion excluded volume and the electrostatic interactions opens new ways for controlling the conformational behavior of polyelectrolytes.