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静电相互作用诱导刚性棒状聚电解质的向列有序:沿链离散电荷分布的影响。

Nematic ordering of rigid rod polyelectrolytes induced by electrostatic interactions: effect of discrete charge distribution along the chain.

机构信息

Department of Mathematics, College of William and Mary, Williamsburg, Virginia 23187, USA.

出版信息

J Chem Phys. 2011 Feb 21;134(7):074901. doi: 10.1063/1.3554746.

Abstract

Similar to the Debye-Hückel plasma, charged groups in solutions of rigid rod polyelectrolytes attract each other. We derive expression for the correlation free energy of electrostatic attraction of the rods within the random phase approximation. In this theory, we explicitly take into account positions of charged groups on the chains and examine both charge and polymer concentration fluctuations. The correlation free energies and the osmotic pressures are calculated for isotropic and completely ordered nematic phase. The results of the discrete model are compared with results of a continuous model. The discrete model gives rise to a stronger attraction between the charged groups both in the isotropic and nematic phases and to a stronger orienting action of the electrostatic forces.

摘要

类似于 Debye-Hückel 等离子体,溶液中刚性棒状聚电解质的带电基团相互吸引。我们在随机相位近似下推导出了棒状聚电解质的静电吸引的相关自由能的表达式。在该理论中,我们明确考虑了带电基团在链上的位置,并同时考察了电荷和聚合物浓度的涨落。我们计算了各向同性和完全有序向列相的相关自由能和渗透压。离散模型的结果与连续模型的结果进行了比较。离散模型导致在各向同性相和向列相中带电基团之间的吸引力更强,并且静电力的定向作用更强。

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