Many-Body Expansion-Based Quantum Mechanical Force Field for Cyclotrimethylene Trinitramine under High Pressure.

RDX undergoes pressures of approximately 30-50 GPa during detonation, leading to significant changes in intermolecular interactions. Accurately describing these interactions is crucial for understanding the energy transfer in the detonation process. To address this, this work introduces a many-body expansion-based quantum mechanical force field (MB-QMFF) to accurately describe RDX's intermolecular interactions under high pressures. Using MB-QMFF, we evaluated various density functionals and found that the M062X functional with GD3 dispersion correction provided the highest accuracy. Regarding intermolecular forces, two-body interactions were the most significant, with three-body interactions being negligible. Additionally, we investigated intermolecular energy variations at different densities (or pressures). The results clearly demonstrate an accurate description of intermolecular interactions by the MB-QMFF scheme. Therefore, we believe that the MB-QMFF scheme can serve as a foundation for the development of RDX-specific force fields and pave the way for future studies on the detonation process of RDX.