An interplay of electrostatic and excluded volume interactions in the conformational behavior of a dipolar chain: theory and computer simulations

Soft Matter. 2018. Vol. 14. P. 3232–3235.

Gordievskaya Y. D., Budkov Y., Kramarenko E. Y.

The effect of an interplay between electrostatic and excluded volume interactions on the conformational behavior of a dipolar chain has been studied theoretically and by means of molecular dynamics simulations. Every monomer unit of the dipolar chain comprises a dipole formed by a charged group of the chain and an oppositely charged counterion.
The counterion is assumed to freelymove around the chain but keeping the distance between oppositely charged ions (the dipole length) fixed. The novelty of the developed mean-field theory is that variations of the dipole parameters (the dipole length and the counterion size) have been accounted for in both electrostatic and excluded volume
contributions to the total free energy of the dipolar chain. It has been shown that conformational transitions between swollen and collapsed states of the chain can be induced by fine-tuning the balance between electrostatic and excluded volume interactions. In particular, in lowpolar media not only globule but also extended coil conformations can be realized even under strong electrostatic attraction. The results ofMD simulations of a dipolar chain with variable dipolar length support theoretical conclusions.

Keywords: Polyelectrolytes, phase separation, Electrostatics, Field-theoretical approaches, Polymer physics, Полиэлектролиты, фазовое расслоение, электростатика, теоретико-полевые подходы, физика полимеров