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Solvation Behavior of Short-chain Polystyrene Sulfonate in Aqueous Electrolyte Solutions: A Molecular Dyamics Study

Journal Article · · Journal of Physical Chemistry B
DOI:https://doi.org/10.1021/jp053512e· OSTI ID:978039

We analyze the solvation behavior of short-chain polystyrene sulfonate (PSS) in aqueous electrolyte solutions by isothernal-isochoric molecular dynamics simulation to determine the solvation effects on the structure and conformation of the polyelectrolyte as a function of the aqueous environment. To that end, we study these aqueous systems including the explicit atomistic description of water, the PSS chain, and their interactions with all species in solution. In addition, we investigate the effect of the degree of sulfonation and its distribution along the PSS chain on the resulting conformation as well as solvation structure. Moreover, we assess the impact of added salts on the net charge of the PSS backbone, placing emphasis on the valence of the counterion and the extent of the ion-pair formation between the sulfonate group and the counterions. Finally, we present evidence for the so-called like-charge attraction between sulfonate groups through the formation of counterion-mediated interchain sulfonate-sulfonate and water-mediated intrachain sulfonate-sulfonate bridges, as well as between unlike counterion-counterion interactions.

Research Organization:
Oak Ridge National Laboratory (ORNL)
Sponsoring Organization:
SC USDOE - Office of Science (SC)
DOE Contract Number:
AC05-00OR22725
OSTI ID:
978039
Journal Information:
Journal of Physical Chemistry B, Journal Name: Journal of Physical Chemistry B Journal Issue: 48 Vol. 109; ISSN 1520-6106
Country of Publication:
United States
Language:
English