Interplay of Polymer Structure, Solvent Ordering, and Charge Fluctuations in Polyelectrolyte Solution Thermodynamics
Interplay of Polymer Structure, Solvent Ordering, and Charge Fluctuations in Polyelectrolyte Solution Thermodynamics
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DOI：
10.1021/acs.macromol.2c01826
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发表时间：
2022-12
期刊：
影响因子：
5.5
通讯作者：
Michael Beckinghausen;A. Spakowitz
中科院分区：
文献类型：
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作者：
Michael Beckinghausen;A. Spakowitz
我们开发了一个聚合物场论模型，该模型包含了对半柔性和极性溶剂的显式处理，提供了一个框架来确定溶剂有序性和浓度波动对聚电解质溶液热力学行为的影响。我们研究了偶极子有序对带电表面附近的静电势的影响以及相反电荷对称聚电解质的相行为。用半柔性聚合物的链结构因子的不同近似确定了包含二次级浓度涨落修正的相图。虽然蠕虫链统计量为相行为提供了最广泛的准确预测，但对于许多实验相关的系统，高斯-刚性内插法仍然是一个足够的近似来进行二次阶涨落修正。然而，我们的理论为预测高阶浓度波动的影响提供了基础，这需要用现有的近似方法无法呈现的链式统计。
We develop a polymer field-theoretic model that incorporates explicit treatment of semiflexibility and polar solvents, providing a framework to determine the impact of solvent ordering and concentration fluctuations on the thermodynamic behavior of polyelectrolyte solutions. We study the effect of dipole ordering on the electrostatic potential near a charged surface and the phase behavior of oppositely charged symmetric polyelectrolytes. The phase diagrams, incorporating quadratic-order concentration fluctuation corrections, are determined using different approximations of the chain structure factor for semiflexible polymers. While wormlike-chain statistics provides the most broadly accurate prediction for phase behavior, a Gaussian-rigid interpolation remains an adequate approximation for quadratic-order fluctuation corrections for many experimentally relevant systems. However, our theory provides the basis for predicting the impact of higher-order concentration fluctuations, which requires chain statistics that cannot be rendered from existing approximate methods.