Physics – Condensed Matter – Soft Condensed Matter
Scientific paper
2001-05-09
Eur. Phys. J. E 5, 97-103 (2001)
Physics
Condensed Matter
Soft Condensed Matter
16 pages, 2 figures
Scientific paper
10.1007/s101890170091
The osmotic coefficient of solutions of rod-like polyelectrolytes is considered by comparing current theoretical treatments and simulations to recent experimental data. The discussion is restricted to the case of monovalent counterions and dilute, salt-free solutions. The classical Poisson-Boltzmann solution of the cell model correctly predicts a strong decrease in the osmotic coefficient, but upon closer look systematically overestimates its value. The contribution of ion-ion-correlations are quantitatively studied by MD simulations and the recently proposed DHHC theory. However, our comparison with experimental data obtained on synthetic, stiff-chain polyelectrolytes shows that correlation effects can only partly explain the discrepancy. A quantitative understanding thus requires theoretical efforts beyond the restricted primitive model of electrolytes.
Ballauff Matthias
Blaul J.
Deserno Markus
Holm Ch.
Rehahn M.
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