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Abstract
A simple model is presented to calculate the potential of mean force between a polyion and a multivalent counterion inside a polyelectrolyte solution. We find that under certain conditions the electrostatic interactions can lead to a strong attraction between the polyions and the multivalent counterions, favouring formation of overcharged polyion–counterion complexes. It is found that small concentrations of salt enhance the overcharging while an excessive amount of salt hinders the charge reversal. The kinetic limitations to overcharging are also examined.
Acknowledgements
This work was supported in part by the Brazilian agencies CNPq and FAPERJ. JFS acknowledges funding by project Pronex-CNPq-FAPERJ/171.168-2003.