James WISHART1, Furong WANG1, Andrew COOK1
1Brookhaven National Laboratory, Upton, United States
Ionic liquids (ILs) have dramatically different properties compared to conventional molecular solvents, and they provide a new and unusual environment to test our theoretical understanding of primary radiation chemistry, charge transfer and other reactions. We are interested in how IL properties influence physical and dynamical processes that determine the stability and lifetimes of reactive intermediates and thereby affect the courses of reactions and product distributions, for example the competition between electron solvation dynamics and the scavenging of electrons in different states of solvation. Pre-solvated electron scavenging is especially significant in ionic liquids because their relatively high viscosities make their solvation dynamics 100-1000x slower than in conventional solvents. Pre-solvated electrons are more mobile and show different reactivity patterns than solvated ones. The slower relaxation dynamics of ILs make them excellent media for the general study of fundamental radiolysis processes, in combination with picosecond pulse radiolysis capabilities such as BNL’s Laser-Electron Accelerator Facility (LEAF). Results will be presented for a wide variety of scavengers (e.g., nitrate, benzophenone) that show different reaction profiles towards the various precursor states to the solvated electron, in ILs of widely different viscosities and dynamics. This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, under contract DE-SC0012704.