Development and application of charge equilibration force fields for the study of aqueous solutions and interfaces.

摘要

This work focuses on the development, validation, and application of polarizable charge equilibration force fields for the study of water and aqueous interfaces. New water models are developed to treat the variation of polarizability in response to the molecule's local environment. Using these models, enhancement of ions at the liquid-vapor interface is observed, emphasizing the importance of solvent polarizability in this phenomenon. Transfer free energetics of water and small molecule alcohols across biologically relevant interfaces is examined and compared to experimental and simulation studies. Additionally, water's role in mediating large scale hydrophobic association is examined. The strength of water-water interactions is shown to correlate with the strength of the hydrophobic interaction. Ions are also shown to influence the strength of the hydrophobic interactions, with different ions acting through separate mechanisms. Results of this work highlight how water polarizability influences water's behavior in various physical systems. Future refinements to the modes used in this work and additional applications are suggested.