Bottom-up coarse-grain modeling of plasticity and nanoscale shear bands in α-RDX

Computationally inexpensive particle-based coarse-grained (CG) models are essential for use in molecular dynamics (MD) simulations of mesoscopically slow cooperative phenomena, such as plastic deformations in solids. Molecular crystals possessing complex symmetry present enormous practical challenges for particle-based coarse-graining at molecularly resolved scales, when each molecule is in a single-site representation, and beyond. Presently, there is no published pairwise non-bonded single-site CG potential that is able to predict the space group and structure of a molecular crystal. In this paper, we present a successful coarse-graining at a molecular level from first principles of an energetic crystal, hexahydro-1,3,5-trinitro-s-triazine (RDX) in the alpha phase, using the force-matching-based multiscale coarse-graining (MSCG/FM) approach. The new MSCG/FM model, which implements an optimal pair decomposition of the crystal Helmholtz free energy potential in molecular center-of-mass coordinates, was obtained by force-matching atomistic MD simulations of liquid, amorphous, and crystalline states and in a wide range of pressures (up to 20 GPa). The MSCG/FM potentials for different pressures underwent top-down optimization to fine-tune the mechanical and thermodynamic properties, followed by consolidation into a transferable density-dependent model referred to as RDX-TC-DD (RDX True-Crystal Density-Dependent). The RDX-TC-DD model predicts accurately the crystal structure of alpha-RDX at room conditions and reproduces the atomistic reference system under isothermal (300 K) hydrostatic compression up to 20 GPa, in particular, the Pbca symmetry of alpha-RDX in the elastic regime. The RDX-TC-DD model was then used to simulate the plastic response of uniaxially ([100]) compressed alpha-RDX resulting in nanoscale shear banding, a key mechanism for plastic deformation and defect-free detonation initiation proposed for many molecular crystalline explosives. Additionally, a comparative analysis of the effect of core-softening of the RDX-TC-DD potential and the degree of molecular rigidity in the all-atom treatment suggests a stress-induced short-range softening of the effective intermolecular interaction as a fundamental cause of plastic instability in alpha-RDX. The reported RDX-TC-DD model and overall workflow to develop it open up possibilities to perform high quality simulation studies of molecular energetic materials under thermal and mechanical stimuli, including extreme conditions.