(199c) Effect Of Molecular Interactions In Gas-Expanded Liquids On Reaction And Electronic Phenomena

A synergistic combination of computational and experimental techniques facilitates the use of gas expanded liquids (GXLs) as a reaction and extraction medium. GXLs are the next generation of tunable solvents offering pressure tunable properties and an inherent separation mechanism, unfortunately their use has been hindered by insufficient knowledge of fluid structure and molecular-scale interactions. GXLs are mixed solvents formed by the addition of a gas, usually CO2, to a traditional organic solvent. As a result, GXLs operate at lower pressures and offer better solvating power than other high pressure solvents like supercritical fluids. We have applied molecular dynamics simulations and spectroscopy to explore fluid structure and solute-solvent interactions in GXLs and have applied our findings to explore the kinetics and equilibrium distribution of two different isomerizations. This work lays the foundation for more complex reaction systems and allows us to optimize solvent parameters for different applications.