The Statistical Mechanics of Electronic Structure in Condensed Phases

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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.