Field-Theoretic Simulations: Polarization Phenomena and Coherent States

该奖项支持理论研究，软件开发和教育，旨在了解两大类新兴的软材料：含离子聚合物和超分子聚合物。这些材料在电池、燃料电池、轻型车辆和飞机等新兴技术领域具有很大的前景。聚合物是大的线性分子，以塑料、橡胶和纺织品的形式在日常生活中无处不在。然而，它们的性质和加工行为可以通过沿其主链沿着离子（电荷）的掺入，或通过引入可以参与可逆化学键（例如氢键）的小化学单元而显著改变。 该项目旨在开发必要的理论和计算机模拟工具，以了解这些系统的物理特性，并定制它们的应用。这两种类型的聚合物系统都违背了传统的理论和计算方法，无论是因为大尺寸和高浓度的聚合物，或静电相互作用和可逆键的复杂性。这个项目将通过使用从理论物理文献改编的“场论”框架来模拟聚合物来解决这些困难。PI将进一步开发数值算法，使聚合物场理论模型的有效计算机模拟。从项目中产生的基本理解和软件工具将加速这类迷人的软材料的合理设计。拟议研究的更广泛影响包括继续参与研究生，本科生和博士后理论和计算聚合物科学的培训。理论导向的学生将通过与UCSB化学工程，材料和化学实验组的紧密结合，接触更广泛的软材料学科。在拟议项目下获得的知识将通过UCSB的复杂流体设计联盟加以利用，该联盟是一个行业-国家实验室-学术合作伙伴关系，致力于商业相关聚合物配方的计算设计。参与者将进一步为UCSB材料研究科学与工程中心充满活力的教育和推广计划做出贡献。技术总结该奖项支持理论研究，软件开发和教育，旨在了解两大类新兴的软材料：含离子聚合物和超分子聚合物本项目将建立在“场论模拟”方法的PI的最新发展基础上，使得能够直接数值研究聚合物和软材料的场论模型，而无需诉诸平均场近似。拟议的研究旨在通过提供一个计算效率高的框架，使理解和方法的根本性，变革性的进步，在该框架中，电荷相关性和极化现象可以在场论模型中进行探索，而无需近似。这将使对广泛种类的含离子、不均匀软物质的突破性研究成为可能。第二个推力涉及发展的“相干态”场理论表示的超分子聚合物模型和强大的数值模拟方法。这样的模拟将提供全面的指导方针，了解在这个复杂的和新兴的一类material.In极化场理论的背景下，模型和有效的算法的自组装和超分子键合平衡的相互作用将被开发用于模拟聚合物系统包含离子，永久偶极子，和极化段。这些将被用来研究含离子的嵌段共聚物，离聚物和聚合物离子液体，和非均相双金属配合物的结构和相行为。电场诱导的现象在这些重要类别的系统将进一步阐明。第二个推力涉及相干态聚合物场理论，一个长期被忽视的相互作用的聚合物的表示受到二次量子化场论的启发。拟议的工作旨在开发和优化算法的相干态模型的模拟和应用这些算法的可逆键合，超分子聚合物的基础研究。这项工作将探索变量之间的关系，如键合平衡常数，化学计量和聚合物结构，自组装行为和热力学性质。重点将放在多组分，非均匀的超分子系统，其中很少的理解和材料设计的指导方针存在。更广泛的影响，拟议的研究包括继续参与研究生，本科生和博士后的理论和计算聚合物科学的培训。理论导向的学生将通过与UCSB化学工程，材料和化学实验组的紧密结合，接触更广泛的软材料学科。在拟议项目下获得的知识将通过UCSB的复杂流体设计联盟加以利用，该联盟是一个行业-国家实验室-学术合作伙伴关系，致力于商业相关聚合物配方的计算设计。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

NONTECHNICAL SUMMARYThis award supports theoretical research, software development, and education aimed at understanding two broad classes of emerging soft materials: ion-containing polymers and supramolecular polymers. These are materials that have great promise in emerging technology areas such as batteries, fuel cells, and lightweight vehicles and aircraft. Polymers are large, linear molecules that are ubiquitous in daily life in the form of plastics, rubbers, and textiles. However, their properties and processing behavior can be significantly changed by the incorporation of ions (electrical charges) along their backbones, or by the introduction of small chemical units that can participate in reversible chemical bonds, such as hydrogen bonds. This project aims to develop the theoretical and computer simulation tools necessary to understand the physical properties of these systems and to tailor them for applications.Both types of polymer systems have defied conventional theoretical and computational approaches either because of the large size and high concentration of the polymers, or the complexity of the electrostatic charge interactions and reversible bonds. This project will tackle these difficulties by modeling the polymers using "field theory" frameworks adapted from the theoretical physics literature. The PIs will further develop numerical algorithms that enable efficient computer simulations of the polymer field theory models. The fundamental understanding and the software tools emerging from the project will accelerate the rational design of this fascinating class of soft materials.Broader impacts of the proposed research include a continuance of the PIs' involvement in graduate, undergraduate, and post-doctoral training in theoretical and computational polymer science. Theoretically-oriented students will be exposed to broader soft materials disciplines through a close coupling with experimental groups at UCSB in chemical engineering, materials, and chemistry. The knowledge gained under the proposed project will be leveraged through the Complex Fluids Design Consortium at UCSB, an industry-national lab-academic partnership that is addressing the computational design of commercially relevant polymer formulations. The participants will further contribute to the vibrant education and outreach programs of UCSB's Materials Research Science and Engineering Center.TECHNICAL SUMMARYThis award supports theoretical research, software development, and education aimed at understanding two broad classes of emerging soft materials: ion-containing polymers and supramolecular polymers This project will build on recent developments by the PIs of the "field-theoretic simulation" method, enabling direct numerical investigations of field theory models of polymers and soft materials without resorting to the mean-field approximation. The proposed research aims to make fundamental, transformative advances in understanding and methodology by providing a computationally efficient framework in which charge correlation and polarization phenomena can be explored without approximation in field-theoretic models. This will enable breakthrough studies of broad classes of ion- containing, inhomogeneous soft matter. A second thrust involves the development of "coherent states" field theory representations of supramolecular polymer models and robust numerical methods for simulating them. Such simulations will provide comprehensive guidelines for understanding the interplay of self-assembly and supramolecular bonding equilibria in this complex and emerging class of materials.In the context of polarizable field theory, models and efficient algorithms will be developed for simulating polymeric systems containing ions, permanent dipoles, and polarizable segments. These will be used to investigate the structure and phase behavior of ion-containing block copolymers, ionomers and polymeric ionic liquids, and inhomogeneous polyelectrolyte complexes. Electric field-induced phenomena in these important classes of systems will be further elucidated.The second thrust relates to coherent-states polymer field theory, a long neglected representation of interacting polymers inspired by second-quantized field theory. The proposed work aims to develop and optimize algorithms for simulations of coherent states models and apply those algorithms to fundamental studies of reversibly bonding, supramolecular polymers. The work will explore relationships between variables such as bonding equilibrium constants, stoichiometry and polymer architecture, and self-assembly behavior and thermodynamic properties. A focus will be on multi-component, inhomogeneous supramolecular systems, for which little understanding and few material design guidelines exist.Broader impacts of the proposed research include a continuance of the PIs' involvement in graduate, undergraduate, and post-doctoral training in theoretical and computational polymer science. Theoretically-oriented students will be exposed to broader soft materials disciplines through a close coupling with experimental groups at UCSB in chemical engineering, materials, and chemistry. The knowledge gained under the proposed project will be leveraged through the Complex Fluids Design Consortium at UCSB, an industry-national lab-academic partnership that is addressing the computational design of commercially relevant polymer formulations. The participants will further contribute to the vibrant education and outreach programs of UCSB's Materials Research Science and Engineering Center.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.