Abstract
Understanding the structural, geometrical and
chemical changes that occur after electronic excitation is essential to unraveling
the inherent physical and chemical mechanisms of nitro
explosives. In
this work, the relaxed structure of some typical nitro explosives in the
excited state, including RDX, HMX, CL-20, PETN and LLM-105, have been
investigated by time-dependent density functional theory. During the excitation
process, an electron is vertically excited into a low-lying excited state, imparting
π-antibonding character onto
the nitro group. The nitro group
becomes activated by the excitation energy and then relaxes via vibrational
cooling, leading to a relaxed excited-state structure. All five nitro explosives exhibit similar
behavior in which impact sensitivity is related to the excitation energy of the
relaxed structure. Insight into the relaxed
structure of typical nitro explosives offers an efficient method of unraveling
ultrafast and complex photo-initiated reactions and detonation physics.