Density functional study of the structure and some decomposition reactions of the dinitramide anion

We have used a non-local density functional procedure (DF/GGA/DZVPP) to compute the structure of the dinitramide anion N(NO& and the energetics of some possible decomposition steps. The structures are in good agreement with crystallographic results, and show the NO2 groups to be rotated out of the N-N-N plane, with a considerable difference between the two N-N-O angles of each NO* group. Of three possible N-N bond breaking reactions, we find that the least energy is required to yield NNOT and NO2 (49.8 kcal mol-‘). We suggest that these products have the option of forming a loosely bound complex.