Surface-Enhanced Decomposition Kinetics of Molecular Materials Illustrated with Cyclotetramethylene-tetranitramine

First principles total energy calculations were combined with variational transition state theory to reveal a surface-induced effect on the decomposition of a molecular material. Explored decomposition reactions were illustrated with energetic molecular solid β-cyclotetramethylene-tetranitramine. Simulated N–NO2 homolysis reactions demonstrated that initiation of molecular material's degradation is characterized by a reduced activation barrier and significantly accelerated reaction rates for molecules that are placed on a free surface, an internal void, or a vacancy as compared to the perfect bulk crystal.