•The binding energy of the ‘top’ mode is greater than that of the ‘side’ mode.•Electron transfer ability of the ‘top’ mode is weaker than that of the ‘side’ mode.•GFP/H+ and GFP/NH4+ interactions cause GFP to be easily oxidized.•Interactions are affected by AP grain size and AP crystal surface direction.In order to explore the interaction mechanism between 2,2-Bis (ethylferrocenyl) propane (GFP) and ammonium perchlorate (AP) at low temperature (below 250 °C), all the possible intermolecular interactions between GFP and AP were calculated. The calculations were performed in single molecule, cluster and slab models. The calculation results show that the interactions between GFP and AP at low temperature mainly come from GFP–H+GFP–H+ and GFP–NH4+ pair interactions. We speculate that the interaction mechanism between GFP and AP at low temperature is that GFP/H+ or GFP/NH4+ interactions cause GFP to be protonated, and then protonated GFP is to further oxidized.All the possible intermolecular interactions between 2,2-Bis (ethylferrocenyl) propane and AP were calculated in single molecule, cluster and slab models.

•A method that analyzed the formation driving force of the cocrystal was proposed.•The driving force of the CL-20 cocrystal formation was concluded.•The reasons for the decreased sensitivity of the CL-20 cocrystals were analyzed.Methods that analyze the driving force in the formation of the new energetic cocrystal are proposed in this paper. Various intermolecular interactions in the 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclo [5.5.0.05,9.03,11]dodecane (CL-20) cocrystals are compared with those in pure CL-20 and coformer crystals by atom in molecule (AIM) and Hirshfeld surface methods under the supramolecular cluster model. The driving force in the formation of the CL-20 cocrystals is analyzed. The main driving force in the formation of the cocrystal CL-20/HMX comes from the O···H interactions, that in the formation of the cocrystal CL-20/TNT from the O···H and C···O interactions, and that in the formation of the cocrystal CL-20/BTF from the N···H and N···O interactions. Other interactions in the CL-20 cocrystals only contribute to their stabilization. At the same time, the reasons for the decreased impact sensitivity of the CL-20 cocrystals are also analyzed. They are the strengthening of the intermolecular interactions, the reducing of the free space, and the changing of the surrounding of CL-20 molecule in the CL-20 cocrystals in comparison with those in the pure CL-20 crystal.