Structural Properties of HEHN- and HAN-Based Ionic Liquid Mixtures: A Polarizable Molecular Dynamics Study

Abstract

Molecular dynamics simulations of binary mixtures comprising 2-hydroxyethylhydrazinium nitrate (HEHN) and hydroxylammonium nitrate (HAN) were conducted using the polarizable APPLE&P force field to investigate fundamental properties of multimode propulsion (MMP) propellants. Calculated densities as a function of temperature were in good agreement with experiments and similar simulations. The structural properties of neat HEHN and HAN–HEHN provided insights into their inherent, protic nature. Radial distribution functions (RDFs) identified key hydrogen bonding sites located at N–H···O and O–H···O within a first solvation shell of approximately 2 Å. Angular distribution functions further affirmed the relatively strong nature of the hydrogen bonds with nearly linear directionality. The increased hydroxylammonium cation (HA+) mole fraction shows the influence of competitively strong hydrogen bonds on the overall hydrogen bond network. Dominant spatial motifs via three-dimensional distribution functions along with nearly nanosecond-long hydrogen bond lifetimes highlight the local bonding environment that may precede proton transfer reactions.