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arXiv · 1501.01235

A new equation of state of a flexible-chain polyelectrolyte solution: Phase equilibria and osmotic pressure in the salt-free case

Yu. A. Budkov·A. L. Kolesnikov·N. Georgi·E. A. Nogovitsyn·M. G. Kiselev
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Abstract

We develop a first-principle equation of state of salt-free polyelectrolyte solution in the limit of infinitely long flexible polymer chains in the framework of a field-theoretical formalism beyond the linear Debye-Hueckel theory and predict a liquid-liquid phase separation induced by a strong correlation attraction. As a reference system we choose a set of two subsystems - charged macromolecules immersed in a structureless oppositely charged background created by counterions (polymer one component plasma) and counterions immersed in oppositely charged background created by polymer chains (hard-core one component plasma). We calculate the excess free energy of polymer one component plasma in the framework of Modified Random Phase Approximation, whereas a contribution of charge densities fluctuations of neutralizing backgrounds we evaluate at the level of Gaussian approximation. We show that our theory is in a very good agreement with the results of Monte-Carlo and MD simulations for critical parameters of liquid-liquid phase separation and osmotic pressure in a wide range of monomer concentration above the critical point, respectively.

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Yu. A. Budkov, A. L. Kolesnikov, N. Georgi, E. A. Nogovitsyn, M. G. Kiselev. 2015-08-03. A new equation of state of a flexible-chain polyelectrolyte solution: Phase equilibria and osmotic pressure in the salt-free case. https://doi.org/10.1063/1.4919251

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