Ability of the Poisson-Boltzmann equation to capture molecular dynamics predicted ion distribution around polyelectrolytes

Here, we examine polyelectrolyte (PE) and ion chemistry specificity in ion condensation via all-atom molecular dynamics (MD) simulations and assess the ability of the Poisson-Boltzmann (PB) equation to describe the ion distribution predicted by the MD simulations. The PB model enables the extraction of parameters characterizing ion condensation. We find that the modified PB equation which contains the effective PE radius and the energy of the ion-specific interaction as empirical fitting parameters describes ion distribution accurately at large distances but close to the PE, especially when strongly localized charge or specific ion binding sites are present, the mean field description of PB fails. However, the PB model captures the MD predicted ion condensation in terms of the Manning radius and fraction of condensed counterions for all the examined PEs and ion species. We show that the condensed ion layer thickness in our MD simulations collapses on a single master curve for all the examined simple, monovalent ions (Na+, Br+, Cs+, Cl-, and Br-) and PEs when plotted against the Manning parameter (and consequently the PE line charge density). The significance of this finding is that, contrary to the Manning radius extracted from the mean field PB model, the condensed layer thickness in the all atom detail MD modelling does not depend on the PE chemistry or counterion type. Furthermore, the fraction of condensed counterions in the MD simulations exceeds the PB theory prediction. The findings contribute toward understanding and modelling ion distribution around PEs and other charged macromolecules in aqueous solutions, such as DNA, functionalized nanotubes, and viruses.