The Statistical Mechanics of Electronic Structure in Condensed Phases

在物理化学计划的理论和计算化学子计划的这个项目中，Stratt将开发一种适用于处理凝聚相电子结构问题的分析统计力学方法。在小分子的电子结构和纯晶体固体的能带结构的研究的极端之间，存在着大量的化学系统，对于这些系统，电子性质只能根据凝聚相可能的行为的丰富性来理解。这种多样性的例子包括从溶剂引起的光谱漂移到在混合价络合物晶体中观察到的相变；从简单膨胀的液态金属的金属-绝缘体转变到液体半导体中看到的各种液体结构和电子特征。借助新发展的路径积分方法和分析流体理论，可以建立和求解这些高度量子力学问题的模型，就像它们是经典统计力学中的练习一样。我们的计划是利用这样得出的见解来重新思考目前基于气相的对分子间相互作用的态度，以及它们可能导致的宏观现象。

In this project in the Theoretical and Computational Chemistry Subprogram of the Physical Chemistry Program, Stratt will develop an analytical statistical mechanical method suitable for treating electronic-structure-in-condensed-phase problems. Between the well-studied extremes of the electronic structure of small molecules and the band structure of pure crystalline solids, lie a large number of chemical systems for which the electronic properties can only be understood in terms of the richness of behavior possible for a condensed phase. Examples of this diversity range from solvent-induced spectral shifts to the phase transitions observed in crystals of mixed-valence complexes; from the metal-insulator transitions of simple expanded liquid metals to the wide variety of liquid structures and electronic characteristics seen in liquid semiconductors. With the aid of newly developed path integral methods and analytical liquid theories, models for each of these highly quantum mechanical problems can be formulated and solved as if they were exercises in classical statistical mechanics. Theplan is to use the insights so derived to enable a rethinking of current gas-phase-based attitudes towards intermolecular interactions and the macroscopic phenomena they can lead to.