Anisotropy in surface-initiated melting of the triclinic molecular crystal 1,3,5-triamino-2,4,6-trinitrobenzene: A molecular dynamics study

Abstract

Surface-initiated melting of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), a triclinic molecular crystal, was investigated using molecular dynamics simulations. Simulations were performed for the three principal crystallographic planes exposed to vacuum, with the normal vectors to the planes given by b × c, c × a, and a × b (where a, b, and c define the edge vectors of the unit cell), denoted as (100), (010), and (001), respectively. The best estimate of the normal melting temperature for TATB is 851 ± 5 K. The nature and extent of disordering of the crystal-vacuum interface depend on the exposed crystallographic face, with the (001) face exhibiting incomplete melting and superheating. This is attributed to the anisotropy of the inter-molecular hydrogen bonding and the propensity of the crystal to form stacking faults in directions approximately perpendicular to the (100) and (010) faces. For all three crystal orientations, formation of molecular vacancies in the lattice at the crystal-vacuum (or crystal-quasi-liquid layer) interface precedes the complete loss of order at the interface.