Fj. Owens, CALCULATION OF ENERGY BARRIERS FOR BOND RUPTURE IN SOME ENERGETIC MOLECULES, Journal of molecular structure. Theochem, 370(1), 1996, pp. 11-16
A calculation of the energy for bond rupture for a number of energetic
molecules using MNDO/3 indicates that the weakest bond is generally t
hat between the NO2 and the remainder of the molecule. A calculation o
f the energy barrier against R-NO2 scission in 26 molecules shows that
there is correlation between the size of the energy barrier and the s
usceptibility to high-rate exothermic reaction (detonation). The corre
lation seems to be independent of bond type (C-N, N-N, O-N) and thus i
ndependent of chemical family. The results suggest that R-NO2 rupture
may be the rate-controlling step in the initiation of detonation of ma
ny energetic molecules.