复杂流体中有效静电相互作用的统计热力学研究

Effective electrostatic interaction is primary force dominating over thermodynamic behavior of soft matter. In the present project, we plan to (1) systematically investigate the effective electrostatic interactions between two colloidal particles involving surface with chemical, geometrical, charge inhomogeneities and immersed in suspension medium containing polyelectrolytes and zwitter-ions by programming for the classical density functional theory codes in two- and three-dimensional spaces; at the same time, define scope of application of controversial traditional theories and Derjaguin approximation. Based on so abundant empirical materials, further refine physical picture of a hydrogen bonding style mechanism suggested recently by the applicant (Zhou, 2013) to explain the like-charged attraction, and develop the hydrogen bonding style mechanism into a general explanation frame for the effective electrostatic interactions. (2) develop the "coupling parameter expansion thermodynamic perturbation framework (Zhou, 2006)" and "non hard sphere perturbation new concept (Zhou, 2009)" to be applicable to solid phase and thermodynamic systems consisting of particles interacting through asymmetric interaction potentials, and as a result, advance the liquid theory to a new stage where thermodynamic systems comprised of anisotropic particles can be dealt with. A combination of the two works mentioned above enables one to predict structures and phase behaviors of colloid suspensions with surface inhomogeneities from the microscopic particle interactions, and thus a microscopic statistical thermodynamic theory is formulated to deal with real complex fluids.

有效静电相互作用是支配软物质热力学行为的主要作用力。本项目拟:1通过编制二维、三维经典密度泛函理论程序代码而系统地研究胶粒表面化学、几何、电荷非均一性、及悬浮液中含聚电解质、两性离子等对胶粒间有效静电相互作用的影响，同时界定有争议的传统理论与Derjaguin近似的适用范围。在此基础上,进一步完善申请人最近针对"象电荷吸引"而提出的氢键型机理(Zhou,2013)之物理图象,从而将之发展为有效静电相互作用的普遍解释框架.2将申请人于前二个项目中提出并发展的"偶合参数展开热力学摄动框架(Zhou,2006)"与"非硬球摄动新概念(Zhou,2009)"发展到固相与能有效处理非对称相互作用势粒子组成的体系，从而将液体理论推进到能处理各向异性粒子热力学体系的新阶段.上述两项工作的结合即能从悬浮介质粒子间微观相互作用势预言表面非均一性胶粒悬浮液结构与相行为,从而提出一套真实复杂流体统计热力学理论。

有效静电相互作用是支配软物质热力学行为的主要作用力。本项目:1通过编制二维、三维经典密度泛函理论程序代码而系统地研究胶粒表面化学、几何、电荷非均一性、及悬浮液中含聚电解质、两性离子、混合电解质等对胶粒间有效静电相互作用的影响，同时界定有争议的传统理论与Derjaguin近似的适用范围。在此基础上,进一步完善申请人最近针对“象电荷吸引”而提出的氢键型机理(Zhou,2013)之物理图象,从而将之发展为有效静电相互作用的普遍解释框架.2将申请人于前二个项目中提出并发展的"偶合参数展开热力学摄动框架(Zhou,2006)"与"非硬球摄动新概念(Zhou,2009)"发展到固相与能有效处理非对称相互作用势粒子组成的体系，从而将液体理论推进到能处理各向异性粒子热力学体系的新阶段.综合上述两项工作，本项目提出了一套真实复杂流体统计热力学理论，能从悬浮介质粒子间微观相互作用势预言表面非均一性胶粒悬浮液结构与相行为。