Design of Energetic Ionic Liquids

An essential need of the US Air Force is the discovery, development, and fielding of new, energetic materials for advanced chemical propulsion in space and missile applications. Some of the key factors driving the requirement for new chemical propellants include: (a) improved performance in terms of increased specific impulse and density, (b) reduced sensitivity to external stimuli such as impact, friction, shock, and electrostatic discharge, and (c) mitigation of environmental and toxicological hazards (and the resulting costs) associated with currently used propellants. A class of compounds, which can potentially meet these requirements is known as ionic liquids (ILs), which are chemical salts with unusually low melting points. The physical and chemical properties of ILs render them useful for many purposes, most notably as environmentally benign ("green") solvents/reaction media but also as catalysts, electrolytes, etc. From a Department of Defense (DoD) perspective, ILs are being explored as new propellants, explosives, and munitions. The Air Force, in particular, is interested in ILs as potential replacements for currently used monopropellants such as hydrazine-which is carcinogenic, highly toxic, and has relatively modest performance characteristics. In contrast, many ILs have superior densities and specific impulses as well as significantly reduced sensitivity and toxicity characteristics. Furthermore, their properties can be carefully tuned via the choice of the component ions. The overall objective of the Design of Energetic Ionic Liquids Challenge Project is to address several key technical issues and challenges associated with the characterization, design, and development of ILs as new monopropellants. Among these, for example, are a fundamental understanding of the (in)stability of ILs, the intrinsic nature of the short- and long-range structure and interactions between the component ions, and identification of the key steps in the initial stages of decomposition and combustion. A hierarchy of computational approaches is employed, including atomistic, high-level quantum chemical methods applied to individual ions and ion clusters, condensed phase atomistic molecular dynamics simulations utilizing polarizable force fields, and mesoscale-level simulations of bulk ionic liquids based upon multiscale coarse graining techniques.