Study of elastic anisotropy for 1, 3, 5-trinitro-1, 3, 5-triazacyclohexane by supramolecular structural unit

Abstract

The relation between elastic property and crystal structure provides a foundation for designing new materials with desired properties and understanding the chemical decomposition and explosion of energetic materials. The supramolecular structural unit is proposed as the smallest chemical unit to quantitatively characterize the elastic anisotropy of 1, 3, 5-trinitro-1, 3, 5-triazacyclohexane (RDX). The supramolecular structural unit refers to the nearest-neighbor coordination polyhedron of one molecule. The supramolecular structural unit of RDX is composed of 15 molecules, and analyzed by the total molecular number density and the density of intermolecular interactions. The elastic modulus model is established on the assumption that 1) the RDX molecule is of sphere and rigid-body; 2) the intermolecular interaction is regarded as a linear spring, i.e. it is described by a bond-spring model; 3) the molecules are close-packed in the series mode. The elastic modulus model based on the supramolecular structural unit demonstrates that the elastic modulus is intrinsically determined by the total molecular number, the equilibrium distance of the molecular pair, the intermolecular force constant, and the angle between the intermolecular non-bonding interaction and the normal to crystal face. The intermolecular force constant is calculated as the second derivative of the intermolecular interaction with respect to the equilibrium centroid distance. The intermolecular interaction is expressed as the summation of van der Waals and electrostatic interactions calculated by COMPASS (condensed-phase optimized molecular potentials for atomistic simulation studies) II forcefield. The calculated elastic moduli are 21.7, 17.1, 20.1, 19.1, and 15.3 GPa for RDX (100), (010), (001), (210), and (021) crystal faces, respectively. The calculation results are consistent with the theoretical values computed by the density functional theory. Excluding RDX(001), the calculated elastic moduli accord with the experimental results measured by the resonant ultrasound spectroscopy (RUS), impulsive stimulated thermal scattering, Brillouin spectroscopy, and nanoindentation methods. The theoretical value (20.1 GPa) of RDX(001) overestimates the experimental values in a range of 15.9–16.6 GPa. The reason can be attributed to the rigid-body approximation for flexible molecules, in which are ignored the motion and deformation of the ring and NO<sub>2</sub> groups when the external loads are applied to RDX(001). The results suggest that the supramolecular structural unit can be the smallest chemical unit to quantitatively characterize the elastic anisotropy of RDX and the elastic anisotropy is mainly due to the angle between the intermolecular interaction and the normal to crystal face.