Finite-length effects on the coil-globule transition of a strongly charged polyelectrolyte chain in a salt-free solvent.

The nature of coil-globule transition and scaling behavior of a strongly charged polyelectrolyte chain in a solution system with explicit neutralizing counterions and solvent molecules are studied using replica-exchange Monte Carlo simulations, focusing on the effects of finite chain length. The results reveal that at the thermodynamic limit of infinitely long chain length, the coil-globule transition may remain first order. Phase transition temperatures at various ion concentrations are obtained by extrapolating the values obtained at finite chain lengths. Furthermore, it is found that the exponent ν of the radius of gyration, <R(g)(2)> ~ N(2ν), can be slightly larger than 1 under some conditions.