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Seeking high-energy density materials(HEDMs)with large exothermicity,significant kinetic stability is the ultimate target in the related material field.A three-membered ring structure of diazirinone(cyc-N2CO)was first proposed as an HEDMs in 1994.which has large exothermicity(around 100 kcal·mol-1)and a large decomposition barrier to N2+CO(27 kcal·mol-1).Intermolecularpolymerization is a convenient and useful way to obtain new energetic materials.In this work,we have extensively explored four stable dimer-polymerization isomers in the way of intermolecular -polymerization.The decomposition reactions including the kinetic stability and thermodynamic stability were computationally explored by using the methods of B3LYP/6-31G(d).The rate-determining barriers for the isomer 1(a four-membered carbon-oxygen ring)was found to 31.9 Kcal·mol-1and 29.9 Kcal·mol-1,which release 142.2 Kcal·mol-1 and 168.8 Kcal·mol-1 dissociation into 2N2+2CO by the stepwise N2-leaving process at the B3LYP/6-31G(d)and CBS-QB3 levels of theory,respectively.The process of the isomer 1 is endothermic with respect to dissociation into 2 cyc-N2CO.So dimer(isomer 1)may well deserve a synthetic trial for HEDMs.Moreover,the mechanism of trimers and tetramers about N2CO with the stepwise N2-leaving process seems to be most plausible for ideal HEDMs.