Unsupervised Reaction Pathways Search for the Oxidation of Hypergolic Ionic Liquids: 1-Ethyl-3-methylimidazolium Cyanoborohydride (EMIM+/CBH–) as a Case Study

Hypergolic ionic liquids have come under increased study for having several desirable properties as a fuel source. One particular ionic liquid, 1-ethyl-3-methylimidazolium/cyanoborohydride (EMIM+/CBH–), and oxidant, nitric acid (HNO3), has been reported to be hypergolic experimentally, but its mechanism is not well-understood at a mechanistic level. In this computational study, the reaction is first probed with ab initiomolecular dynamics simulations to confirm that anion–oxidant interactions likely are the first step in the mechanism. Second, the potential energy surface of the anion–oxidant system is studied with an in-depth search over possible isomerizations, and a network of possible intermediates are found. The critical point search is unsupervised and thus has the potential of identifying structures that deviate from chemical intuition. Molecular graphs are employed for analyzing 3000+ intermediates found, and nudged elastic band calculations are employed to identify transition states between them. Finally, the reactivity of the system is discussed through examination of minimal energy paths connecting the reactant to various common products from hypergolic ionic liquid oxidation. Eight products are reported for this system: NO, N2O, NO2, HNO, HONO, HNO2, HCN, and H2O. All reaction paths leading to these exothermic products have overall reaction barriers of 6–7 kcal/mol.