Molecular dynamic simulation of the hydration and diffusion of chloride ions from bulk water to polypyrrole matrix

J Chem Phys. 2004 Jan 22;120(4):1951-7. doi: 10.1063/1.1636453.

Abstract

A molecular dynamic simulation of wet polypyrrole film was carried out, in both oxidized and reduced state. The system was modeled by two layers of polypyrrole, water and chloride ions (as counterions required for charge balance in the oxidized state) in atomic detail to provide an insight into some dynamic and steady properties of the system. Our simulations pointed to a swelling of the polymer matrix after oxidation due to electrostatic repulsions between charged sites of the oxidized polypyrrole, followed by penetration of the polypyrrole by counterions to maintain the electroneutrality of the system. Associated with this penetration of counterions toward the core of the oxidized polypyrrole, dehydration of the counterions was observed. This dehydration was compensated (in part) by a strong coordination with the charged sites of the polymer. The remaining hydrophobicity inside the polymer also contributed to the dehydration of these counterions. The translational diffusion coefficient of chloride ions was also calculated at different positions of the polypyrrole/water interface, from bulk water to the inner polymer matrix. A value of 4.1 x 10(-5) cm(2) s(-1) was measured in the bulk water compared to 5 x 10(-7) cm(2) s(-1) inside the polymer, representing a diminution of two orders of magnitude for the translational diffusion coefficient from bulk water to the core of a oxidized polypyrrole matrix. These results were in good agreement with experimental data.