Materials Science and Engineering Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA.
J Chem Phys. 2017 Dec 28;147(24):241103. doi: 10.1063/1.5010784.
We investigate the influence of counter-ion solvation on the homogeneity of salt-free polyelectrolyte solutions based on a coarse-grained model that includes an explicit solvent. We show that the solvation of the counter-ions can cause a transformation between a nearly homogeneous to a non-uniform polymer solution, in which there is both a chain clustering and the formation of large charge-free domains, i.e., "voids." The emergence of these heterogeneous structures induced by counter-ion solvation is accompanied by the localization and formation of counter-ion rich domains that are symptomatic of emergent effective long-range attractive interchain interactions.
我们研究了反离子溶剂化对无盐聚电解质溶液均匀性的影响，该模型基于一个包含显式溶剂的粗粒模型。结果表明，反离子的溶剂化作用会导致聚合物溶液从近乎均匀到不均匀的转变，在这种溶液中，存在链聚集和大的电荷非自由区域（即“空穴”）的形成。反离子溶剂化引起的这些不均匀结构的出现伴随着反离子富集区的局域化和形成，这表明出现了有效的长程吸引力的链间相互作用。
