SGER: Approximate Density Functional Theory for Predicting the Structural and Interfacial Properties of Complex Fluids

“SGER：用于预测复杂流体结构和界面性质的近似密度泛函理论”这项SGER资助旨在基于PI小组在包括聚合物链和模型胶体在内的相对简单系统的分子建模方面的最新成就，建立复杂流体的统一密度泛函理论。初步应用表明，广义密度泛函理论与分子模拟结果非常吻合，包括球形颗粒高度不对称混合物的密度分布、吸附等温线和对相关函数，以及聚合物的分子内和分子间相关函数。为了验证其在具有引力和静电相互作用的现实系统中的应用，该理论将进一步用中性和带电受限流体的模拟和实验数据进行测试。在这项工作中提出的理论方法是探索性的，并且在其公式方面具有很大的创新性，例如最近在PI的小组中提出的排除体积效应和链连通性，基于能量方法的范德华吸引力，以及基于Rosenfeld的新颖变分方法的库仑相互作用。此外，它代表了第一次努力发展一个统一的分子理论，适用于散装和非均匀系统在相同水平的数值精度使用单一的分子参数集。提出的密度泛函理论还将通过基于改进的SPC/E模型的液态水的结构和热力学性质的相关性/预测以及小离子和简单碳氢化合物的溶剂化来验证。广泛的影响：一旦建立，统一密度泛函理论可用于模拟原子和聚合物流体在多孔材料或表面的吸附，这在气体储存，分离，非均相化学反应，环境保护，燃料电池和多孔材料的设计中具有重要意义。特别是，开发一种适用于非均匀条件的可靠的水分子模型在溶液化学、生物和环境科学中具有至关重要的意义。一个可靠的大气气溶胶形成和有机化合物气体/颗粒分配的分子理论对于理解气溶胶对大气化学、人类和生态健康以及气候的影响至关重要。

Wu, JianzhongU of Cal - Riverside "SGER: Approximate Density Functional Theory for Predicting the Structural and Interfacial Properties of Complex Fluids"This SGER grant seeks to establish a unified density functional theory of complexfluids based on recent achievements from the PI's group in molecular modeling of relatively simple systems including polymeric chains and model colloids. Initial applications indicate that the generalized density functional theory agrees very well with molecular simulation results for the density distributions in confined geometries, adsorption isotherms, and pair correlation functions of bulk fluids including those for highly asymmetric mixtures of spherical particles and intra- and inter- molecular correlation functions of polymers. To validate its applications to realistic systems with attractive forces and electrostatic interactions, the theory will be further tested with simulation and experimental data for neutral as well as charged confined fluids.The theoretical approach proposed in this work is exploratory and substantially novel in terms of its formulations for the excluded-volume effect and for the chain connectivity as proposed recently in the PI's group, for van der Waals attractions based on the energy approach, and for the Coulomb interactions based on a novel variational approach by Rosenfeld. Besides, it represents the first effort to develop a unified molecular theory that is applicable to bulk as well as inhomogeneous systems at the same level of numerical accuracy using a single set of molecular parameters.The proposed density functional theory will also be tested by correlation/prediction of the structural and thermodynamic properties of liquid water and the solvation of small ions and simple hydrocarbons based on a modified SPC/E model. Broad Impacts: Once established, the unified density functional theory can be used for modeling adsorptions of atomic as well as polymeric fluids in porous materials or at surfaces that are of importance in gas storage, separations, heterogeneous chemical reactions, environmental protection, fuel cells, and the design of porous materials. In particular, development of a reliable molecular model for water that is applicable to inhomogeneous conditions is of crucial importance in solution chemistry, biological and environmental sciences. A reliable molecular theory for atmospheric aerosol formation and gas/particle partitioning of organic compounds is central to understanding the influence of aerosols on atmospheric chemistry, human and ecological health, and climates.