CHEMISTRY OF ENERGETIC MATERIALS UNDER SHOCK CAUSED VIA ELECTRONIC EXCITATIONS

Abstract

Explosives sensitivity to shock and impact have been related to electronic excitations for the first time, demonstrated by the linear correlation of sensitivity with the shake-up promotion energy observed in x-ray photoelectron spectra. The especial feature of the shake-up spectra is that they arise during the core ionization of the atom in the time frame of 10−14 sec., which is smaller than the transit time of the detonation wave over the dimensions of a molecule. The Coulomb attraction of the ionized state modifies the outer orbitals in ways analogous to those observed from high pressure or shock. The shake-up excitations follow monopole selection rules, resulting in excited states that are normally forbidden. Bond disruptions, free radical formation and molecular alterations may occur from the forbidden states with longer life-time. Analysis of explosives recovered from the verge of ignition due to shock or impact have demonstrated such alterations. The creation of these products through pressure induced electronic excitations is proposed in this work.