AIMS simulation study of ultrafast electronically nonadiabatic chemistry of methyl azide and UV-VIS spectroscopic study of azido-based energetic plasticizer bis(1,3-diazido prop-2-yl)malonate

To gain insight into the ultrafast electronically nonadiabatic chemistry of azido-based energetic plasticizer, we have explored the nonadiabatic chemical dynamics of an azido-based model analog molecule, methyl azide (MAz), using ab initio multiple spawning (AIMS) simulation and electronic structure theory calculations. Molecular nitrogen (N2) is predicted to be the initial product of MAz following its electronic excitation to the S1 electronically excited state. AIMS-based simulation reveals that electronically excited azido-based molecules undergo extremely fast (approximately in 40 femtoseconds) relaxation to the ground state via the (S1/S0)CI conical intersection. Furthermore, this relaxation process involves the NN bond elongation along with the bending of N3 moiety. This is the first report on the electronically non-adiabatic chemical dynamics (in ultrafast time domain) of methyl azide. Finally, using ultraviolet-visible (UV-VIS) spectroscopy, we comment on the electronically nonadiabatic chemistry of azido-based energetic plasticizer, bis(1,3-diazido prop-2-yl)malonate.