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Conformation of single polyelectrolytes in tetravalent salt solutions isinvestigated under the framework of a coarse-grained model, using Langevindynamics simulations. The chain size, studied by the radius of gyration, showsthree different variational behaviors with salt concentration, depending on thechain stiffness. According to these behaviors, polyelectrolytes of fixed chainlength are classified into three categories: flexible chain, semiflexiblechain, and rigid chain. The worm-like chain model with persistence lengthpredicted by the Odijk-Skolnick-Fixman theory is found to be able toqualitatively describe the end-to-end distance at low salt concentration. In alow-salt region, a flexible polyelectrolyte extends more significantly than asemiflexible chain, and in a high-salt region, regardless of chain stiffness, achain attains a dimension comparable to that of its neutral polymer. The chainstiffness influences both the local and the global chain structures. A flexiblechain exhibits a zigzagged local structure in the presence of salt ions and thecondensed structure is a disordered, random globule. A semiflexible chain islocally smooth, and the condensed structure is orderly packed, taking a formsuch as hairpin or toroid. Moreover, the chain stiffness can also affect thenature of the coil-globule transition. The transition is occurred in a discretemanner for semiflexible chain, whereas in a continuous way for flexible chain.This discrete feature is happened not only at low salt concentration when asemiflexible chain is collapsed, but also at high salt concentration when thecollapsed chain is reexpanded. At the end, the effects of chain stiffness andsalt concentration on the conformation of single polyelectrolytes aresummarized in a schematic state diagram.

Role of chain stiffness on the conformation of single polyelectrolytes in salt solutions