Molecules, Vol. 27, Pages 3266: Theoretical Studies on the Role of Guest in α-CL-20/Guest Crystals (Molecules)

The contradiction between energy and safety of explosives is better balanced by the host–guest inclusion strategy. To deeply analyze the role of small guest molecules in the host–guest system, we first investigated the intermolecular contacts of host and guest molecules through Hirshfeld surfaces, 2-D fingerprint plots and electrostatic interaction energy. We then examined the strength and nature of the intermolecular interactions between CL-20 and various small molecules in detail, using state-of-the-art quantum chemistry calculations and elaborate wavefunction analyses. Finally, we studied the effect of the small molecules on the properties of CL-20, using density functional theory (DFT). The results showed that the spatial arrangement of host and guest molecules and the interaction between host and guest molecules, such as repulsion or attraction, may depend on the properties of the guest molecules, such as polarity, oxidation, hydrogen content, etc. The insertion of H2O2, H2O, N2O, and CO2 had significant influence on the electrostatic potential (ESP), van der Waals (vdW) potential and chemical bonding of CL-20. The intermolecular interactions, electric density and crystal orbital Hamilton population (COHP) clarified and quantified the stabilization effect of different small molecules on CL-20. The insertion of the guest molecules improved the stability of CL-20 to different extents, of which H2O2 worked best.