Chemistry of aliphatic unconjugated nitramines. Part 7.—Interrelations between the thermal, photochemical and mass spectral fragmentation of RDX

Abstract

The mass spectral fragmentation of RDX and HMX has been described in terms of their metastable transitions, mass measurements and ionization efficiency curves. The ring migration of an NO₂ group is noted. The known interrelation between the thermal, photochemical and mass spectral fragmentation of RDX is rationalized in terms of the common bond strength inequality CN < NN < NO, which holds for its ground and lowest excited states, as well as the ground and first excited doublet state of its cation. The same rationale applies to s-N, N-dimethyl nitramine and α-and β-HMX.