Initial mechanisms for the unimolecular decomposition of electronically excited nitrogen-rich energetic materials with tetrazole rings: 1-DTE, 5-DTE, BTA, and BTH.

Abstract

Unimolecular decomposition of nitrogen-rich energetic molecules 1,2-bis(1H-tetrazol-1-yl)ethane (1-DTE), 1,2-bis(1H-tetrazol-5-yl)ethane (5-DET), N,N-bis(1H-tetrazol-5-yl)amine (BTA), and 5,5'-bis(tetrazolyl)hydrazine (BTH) has been explored via 283 nm two photon laser excitation. The maximum absorption wavelength in the UV-vis spectra of all four materials is around 186-222 nm. The N2 molecule, with a cold rotational temperature (<30 K), is observed as an initial decomposition product from the four molecules, subsequent to UV excitation. Initial decomposition mechanisms for these four electronically excited isolated molecules are explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanism. The tetrazole ring opens on the S1 excited state and through conical intersections (S1/S0)CI, N2 product is formed on the ground state potential energy surface without rotational excitation. The tetrazole rings of all four energetic molecules open at the N1-N2 ring bond with the lowest energy barrier: the C-N bond opening has higher energy barrier than that for any of the N-N ring bonds. Therefore, the tetrazole rings open at their N-N bonds to release N2. The vibrational temperatures of N2 product from all four energetic materials are hot based on theoretical calculations. The different groups (CH2-CH2, NH-NH, and NH) joining the tetrazole rings can cause apparent differences in explosive behavior of 1-DTE, 5-DTE, BTA, and BTH. Conical intersections, non-Born-Oppenheimer interactions, and dynamics are the key features for excited electronic state chemistry of organic molecules, in general, and energetic molecules, in particular.