Structural properties and the topology of polyelectrolyte complexes (PECs) formed in solution have been investigated under different conditions by Monte Carlo simulations using a coarse-grained model. The extension of individual polyions has been characterized by their radius of gyration, whereas the composition of the complexes has been investigated by their net charge and their internal topological structure by a novel analysis describing how the shorter polycations link to monomers of the longer polyanion. Conditions have been found at which the polyanion and a given number of polycations form distinguishable complexes differing in (i) the polyanion conformation and (ii) the fraction of polycations being in extended and collapsed states. Thus, at equilibrium, these PECs display a stepwise variation of the degree of intrachain disproportionation within the polyanion (also referred to as intrachain segregation), concomitant with the interchain disproportionation of the polycations, which is in agreement with previous theoretical predictions. The coexistence of the different polyelectrolyte complex structures appears, generally, at mixing ratios close to but different from charge equivalence and, as a consequence, broad polyelectrolyte size distributions are commonly obtained.
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