Atomistic understanding of self-healing of a ferroelastic crystal.

The recent discovery of the self-healing capabilities of molecular crystals has shown significant efficiency, approaching nearly 100%, particularly when this process is coupled with a phase transition. This places these materials on par with other, better-studied soft materials, such as polymers. However, the physical inaccessibility of the contact interface with common analytical methods hinders direct experimental observation of the critical molecular-scale processes responsible for the recovery of the interfacial gap; as a result, this effect has largely remained phenomenological. This report employs molecular dynamics simulations and mechanical analysis to unravel the mechanistic details behind the remarkably efficient (95%) self-healing observed in the ferroelastic crystal anilinium bromide. Bulk simulations successfully reproduce the experimentally observed phase transitions under both uniaxial and biaxial loading conditions, while slab model calculations with free surfaces capture crack formation and self-healing phenomena associated with twinning and detwinning. The atomistic insights establish a two-step model: external mechanical loading first activates molecular slip along the (110)[11̄0] path, providing a periodic impulse force that encourages molecular reorientation, leading to twinning and detwinning, along with subsequent ferroelastic and self-healing behaviors. These findings underscore the critical roles of crystal packing and mechanical loading and offer clear design principles for developing new organic self-healing materials with enhanced mechanical properties.