A flexible-molecule force field to model and study hexanitrohexaazaisowurtzitane (CL-20) – polymorphism under extreme conditions

The quantum-chemistry based force field (FF) developed for HMX by Smith and Bharadwaj (SB) [G. D. Smith and R. K. Bharadwaj, J. Phys. Chem. B, 1999, 103(18), 3570–3575] is transferred to another nitramine of different stoichiometry: hexanitrohexaazaisowurtzitane (CL-20 or HNIW). The modification of a single parameter alongside a very small number of add-ons related to carbon–carbon bonds, angles and dihedrals lead to two SB FF variants denoted SB-CL20 and SB-CL20 + CCNN. These flexible-molecule FFs should inherit the predictive capabilities of SB FF. For this purpose, we perform Molecular Dynamics simulations at ambient temperature and selected pressures. The modeled structures of the various CL-20 polymorphs are consistent with experimental data. Focusing on the ε-polymorph, we determine an equation of state which consolidates the general trend underpinned by most published results, and we confirm the increasing stiffness of the crystal under pressures up to 90 GPa. Moreover, we link some subtle pressure-induced changes of the elastic and structural properties to the flexibility and mobility of well-identified nitro groups. Finally, the simulations of the γ ↔ ζ phase transition suggest different multiple-step direct and reverse thermodynamic paths.