The role of charges in determining the water solubility of polyelectrolytes, a question of considerable relevance to biology, is currently unresolved. We use computer simulations to study the purely Coulombic phase separation of flexible polyelectrolytes with monovalent counterions in an athermal solvent. In agreement with recent theories we find that the critical temperature for this transition increases with chain length, but that the critical density remains unchanged. We therefore stress that the phase behavior of polyelectrolytes is qualitatively different from uncharged polymers, where the critical density decreases towards zero for long chains.

• Received 11 July 2002

DOI:https://doi.org/10.1103/PhysRevLett.90.048303