A carbon Auger line shape study of nitroaromatic explosives

Abstract

The C(KVV) Auger line shapes of a series of nitroaromatic explosives have been compared to condensed benzene. Energy shifts of the pi levels in TNB (1,3,5-trinitrobenzene) and TNT (2,4,6-trinitrotoluene) and charge redistribution caused by the resonance electron withdrawing effect of the nitro groups lead to changes in the Auger line shape of transitions involving these levels compared to those of benzene. In MATB (1-amino-2,4,6-trinitrobenzene), DATB (1,3-diamino-2,4,6-trinitrobenzene), and TATB (1,3,5-triamino-2,4,6-trinitrobenzene), the amino groups form resonant structures with the aromatic ring and donate charge density into the ring pi levels. This more than compensates for the charge density withdrawn by the nitro groups. As a result, an amino-carbon pi level is populated which leads to dramatic changes in the energy and intensity of the leading edge of the C(KVV) line shape for these compounds. Hole-hole correlation in the final state causes only small changes in line shape. The relative explosive shock initiation sensitivity of TNB and TNT, where the intermolecular bonding is weak, correlates with the observed Auger line shape changes and reflects the relative ring stability of these aromatic molecules. However, the addition of amino groups in MATB, DATB, and TATB decreases the ring bonding, as reflected in the Auger spectra, in favor of intra- and intermolecular hydrogen bond formation and the initiation sensitivity no longer correlates with ring bonding strength.