Hypergolic ionic liquids (HILs), spontaneous ignition upon contact with an oxidizer, are expected to be non-toxic rocket fuels replacing hydrazine. Designing and tuning ILs while understanding reaction mechanisms at the molecular level is mandatory for their applications. This study comprehensively explored a set of reactions for an anion [N(CN)2]− or [BH2(CN)2]−, reported to be a component of HILs, with HNO3 using the quantum chemical Artificial Force Induced Reaction (AFIR) method. For both cases, electrostatic interactions between HNO3 and anions via protons have triggered the reactions. However, the pathways after the formation of hydrogen-bonded complexes were found to be quite different from each other despite the similarity of the anion structures. Specifically, nucleophilic attack by NO3− was observed for [N(CN)2]−, but not for [BH2(CN)2]−. These differences were explained by the natural resonance theory (NRT); that is, the charge distributions of the anions governed the reaction pathways. A set of energy diagrams and electronic structure analyses is necessary to understand hypergolicity.
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