Dynamical clustering of counterions on flexible polyelectrolytes

Molecular dynamics simulations are used to study the spatiotemporal dynamics of charge fluctuations around a polyelectrolyte molecule at charge densities above and below the classic counterion condensation threshold. Surprisingly, the counterions form weakly interacting clusters which exhibit slowly decaying short range orientational order. Local charge fluctuations create energy fluctuations at the order of kBT that is sufficient to affect the polyelectrolyte interaction with an approaching ligand molecule. The predictions of the classical theory appear to be appropriate only over much longer time scales.