Statistical Mechanics of Dynamics and Structure in Liquids

加州大学伯克利分校的David Chandler得到了理论和计算化学项目的支持，继续他在统计力学方面的研究，旨在理解液体和相关系统的结构和动力学。在第一个项目中，油水表面活性剂系统的电荷受挫模型将用于开发和利用非常不同现象之间的同态性，包括液体溶液中的金属-绝缘体转变和过冷液体的玻璃化。在另一个项目中，将利用小尺度和大尺度的疏水性来发展一种普遍适用的统计场理论。这个公式将被用作大尺度现象学和小尺度复杂流体原子理论之间的桥梁，并用于分析聚合物熔体和混合物以及液晶等系统。这些技术还有望使水和其他相关流体的平衡理论得以发展。在动力学领域，过渡路径采样将用于设计现象学理论弱酸解离和质子转移在水系统。将探讨在过渡路径采样的背景下处理量子效应的方法，目标是实现涉及轻原子（如水中的质子）的动力学的定量处理。在最后的项目中，将进一步发展控制轨迹集合的概念，特别是对于远离平衡的系统。预计结果将能够分析对称性破缺，对应于破缺遍历性和驱动系统的相变。提高对液体系统结构和动力学的认识对基础科学和技术应用具有深远的意义。该项目的成果将影响材料科学，包括聚合物和液晶系统。此外，关于质子转移和疏水效应的新结果将与包括蛋白质折叠在内的生物学相关系统有很强的联系。

David Chandler of the University of California, Berkeley, is supported by the Theoretical and Computational Chemistry Program to continue his research in statistical mechanics directed at understanding structure and dynamics of liquids and related systems. In the first project, charge frustrated models of oil-water-surfactant systems will be used to develop and exploit isomorphisms between very different phenomena, including metal-insulator transitions in liquid solutions and vitrification of supercooled liquids. In another project, hydrophobicity at small and large length scales will be exploited to develop a generally applicable statistical field theory. This formulation will be applied as a bridge between large length scale phenomenology and small scale atomistic theories of complex fluids, and used to analyze systems such as polymer melts and blends, and liquid crystals. These techniques are also expected to enable development of an equilibrium theory for water and other associated fluids. In the area of dynamics, transition path sampling will be used to devise phenomenological theories for weak acid dissociation and proton transfer in aqueous systems. Methods for treating quantum effects within the context of transition path sampling will be explored, with the goal of enabling quantitative treatments of kinetics involving light atoms such as protons in water. In a final project, concepts governing ensembles of trajectories will be developed further, especially for systems far from equilibrium. Outcomes are expected to enable the analysis of broken symmetry, corresponding to broken ergodicity and to phase transitions of driven systems. Improved understanding of liquid systems structure and dynamics has far-reaching implications for fundamental science and technology applications. Outcomes from this project will impact materials science, including polymers and liquid crystal systems. As well, new results on proton transfer and the hydrophobic effect will have strong connections to biologically relevant systems, including protein folding.