强静电耦合聚电解质溶液相行为的理论研究

There emerges a variety of correlation-induced novel phenomena in strongly electrostatic coupled polyelectrolyte solutions, however, most of present theories of polyelectrolyte solutions can only handle the weak coupling case. Although many researchers begin to work on this topic, it remains to be a problem to establish a systematic and effective theory for strong coupling case. This project focuses on the development of theoretical methods of phase behaviors in strongly electrostatic coupled polyelectrolyte solutions in terms of statistical field theory. Four parts are included: (1) Effects of counterion condensation on phase separations of polyelectrolyte solutions; (2) Calculation of inter-chain effective interaction in the strongly coupled system; (3) Electrostatic correlation induced instabilities of polyelectrolyte solutions; (4) Confinement effects in the strongly coupled solution. Effects of polyelectrolyte chain stiffness are incorporated within all the four parts. The project applicant has many experiences in the study of field-theoretic methods in polymer physics and polyelectrolyte theory. Implementation of this project is of very importance to the study of fundamental polyelectrolyte physics, the design of polyelectrolyte materials, and the understanding of related phenomena in life.

强静电耦合条件下聚电解质溶液表现出众多关联效应诱导的新颖现象，而现有的聚电解质溶液理论多数只能处理弱静电耦合情形。虽然大量研究者已经开始投入这一问题的研究，然而目前仍未建立一个系统和有效的强耦合聚电解质溶液理论。本项目致力于利用统计场论发展强耦合聚电解质溶液相行为理论，具体研究内容包括四个方面：（1）反离子凝聚对聚电解质溶液相分离的影响；（2）强静电耦合聚电解质链间相互作用计算；（3）静电关联诱导聚电解质溶液不稳定性；（4）强静电耦合聚电解质溶液受限效应。在四个内容的研究中同时考察聚电解质链刚性效应。项目申请人在高分子物理场论和聚电解质理论研究中有丰富经验，该项目的执行，将对于推动聚电解质基础物理，以及聚电解质材料设计和理解生命相关现象具有重要意义。

聚电解质体系在强静电耦合条件下由静电关联诱导出一系列有趣的现象。本课题致力于发展强静电耦合聚电解质理论，主要研究内容和结果如下：(1) 球状聚电解质刷-多价反离子体系由憎水与静电关联诱导的相分离及有序化，较之于憎水诱导相分离，静电关联诱导相分离形成更有序的结构；(2) 立方状聚电解质刷-多价反离子体系由静电关联诱导的相分离；(3) 环形聚电解质平面刷通过静电关联诱导横向和径向相分离，导致不同尺度的有序结构；(4) 构造了含高阶导数作用量的统计场论以处理静电关联，得到了解析解；(5) 利用发展的统计场论方法，计算了长程关联体系中的临界卡西米尔力，推广了现有的临界卡西米尔力研究。