Initial decomposition pathways of 1,1-diamino-2,2-dinitroethylene (α-FOX-7) in the condensed phase

Abstract

The initial decomposition pathways of α-FOX-7 in the condensed phase (crystal) were investigated via density functional theory. Calculations were carried out using three FOX-7 systems with increasing complexity from 1-layer (sheet) via 2-layer (surface) to 3-layer (bulk). The encapsulated environment of the central α-FOX-7 molecule, where decomposition takes place, is reconstructed by neighbouring molecules following a crystal structure. A minimal number of neighbouring molecules that have an impact on the energetics of decomposition are identified among all surrounding molecules. The results show that the presence of intermolecular hydrogen bonds due to the encapsulated environment in the condensed phase decreases the sensitivity of α-FOX-7, i.e. it increases the barrier of decomposition, but it does not alter the initial decomposition pathways of the reaction compared to the gas phase. Moreover, increasing the complexity of the system from a single gas phase molecule via sheet and surface to bulk increases the decomposition barriers. The calculations reveal a remarkable agreement with experimental data [A. M. Turner, Y. Luo, J. H. Marks, R. Sun, J. T. Lechner, T. M. Klapötke and R. I. Kaiser, Exploring the Photochemistry of Solid 1, 1-Diamino-2, 2-Dinitroethylene (FOX-7) Spanning Simple Bon Ruptures, Nitro-to-Nitrite Isomerization, and Nonadiabatic Dynamics, J. Phys. Chem. A, 2022, 126, 29, 4747–4761] and suggest that the initial decomposition of α-FOX-7 likely takes place at the surface of the crystal.