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

吴建中加州大学滨江分校“SGER：近似密度泛函理论预测复杂流体的结构和界面性质“该SGER基金旨在建立一个统一的密度泛函理论的基础上，从PI的小组在分子模拟相对简单的系统，包括聚合物链和模型胶体的最新成果复杂流体。初步的应用表明，广义密度泛函理论与分子模拟结果在封闭几何中的密度分布、吸附等温线和体相流体的对关联函数，包括高度不对称的球形颗粒混合物的对关联函数以及聚合物的分子内和分子间关联函数等方面吻合得很好.为了验证其在具有吸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以及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PI小组最近提出的排斥体积效应和链连接性方面具有实质性的新颖性。基于能量方法的货车德瓦耳斯吸引力和基于Rosenfeld的新变分方法的库仑相互作用。此外，它代表了第一次努力，开发一个统一的分子理论，适用于散装以及非均匀系统在同一水平的数值精度，使用一套单一的分子参数.建议的密度泛函理论也将通过相关/预测的结构和热力学性质的液态水和溶剂化的小离子和简单的碳氢化合物的基础上修改的SPC/E模型进行测试。广泛影响：一旦建立，统一的密度泛函理论可用于模拟原子以及聚合物流体在多孔材料或表面上的吸附，这些吸附在气体储存、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，一个可靠的水分子模型，适用于非均匀条件下的发展是至关重要的溶液化学，生物和环境科学。大气气溶胶形成和有机化合物的气体/颗粒分配的可靠分子理论是理解气溶胶对大气化学，人类和生态健康以及气候的影响的核心。

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.