Optimal linearized Poisson–Boltzmann (OLPB) theory is applied to the simulation of flexible polyelectrolytes in solution. As previously demonstrated in the contexts of the cell model [H. H. von Grünberg, R. van Roij, and G. Klein, Europhys. Lett. 55, 580 (2001)] and a particle-based model [B. Beresfordsmith, D. Y. C. Chan, and D. J. Mitchell, J. Colloid Interface Sci. 105, 216 (1985)] of charged colloids, OLPB theory is applicable to thermodynamic states at which conventional, Debye–Hückel (DH) linearization of the Poisson–Boltzmann equation is rendered invalid by violation of the condition that the electrostatic coupling energy of a mobile ion be much smaller than its thermal energy throughout space, As a demonstration of its applicability to flexible polyelectrolytes, OLPB theory is applied to a concentrated solution of freely jointed chains. The osmotic pressure is computed at various reservoir ionic strengths and compared with results from the conventional DH model for polyelectrolytes. Through comparison with the cylindrical cell model for polyelectrolytes, it is demonstrated that the OLPB model yields the correct osmotic pressure behavior with respect to nonlinear theory where conventional DH theory fails, namely at large ratios of mean counterion density to reservoir salt density, when the Donnan potential is large.
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22 October 2004
Letter|
October 22 2004
Optimal linearized Poisson–Boltzmann theory applied to the simulation of flexible polyelectrolytes in solution
M. Bathe;
M. Bathe
Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139
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A. J. Grodzinsky;
A. J. Grodzinsky
Department of Electrical Engineering and Computer Science, Department of Mechanical Engineering, and Biological Engineering Division, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139
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B. Tidor;
B. Tidor
Department of Electrical Engineering and Computer Science and Biological Engineering Division, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139
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G. C. Rutledge
G. C. Rutledge
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139
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J. Chem. Phys. 121, 7557–7561 (2004)
Article history
Received:
June 24 2004
Accepted:
August 30 2004
Citation
M. Bathe, A. J. Grodzinsky, B. Tidor, G. C. Rutledge; Optimal linearized Poisson–Boltzmann theory applied to the simulation of flexible polyelectrolytes in solution. J. Chem. Phys. 22 October 2004; 121 (16): 7557–7561. https://doi.org/10.1063/1.1808411
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