Theoretical investigations on the stability of alkali metal substituted phenylpentazole.

The alkali metal (M=Li, Na, and K) para-substituted (M-1), meta-substituted (M-2) or ortho-substituted (M-3) derivatives of phenylpentazole (PhN5) were studied using density functional theory. The substituted metals improve the energy barrier for decomposition of the N5 ring of PhN5 by 19.3 ∼ 65.0 kJ/mol. M-3 has the ionic N-M bond, which is not found for M-1 and M-2. M-1 and M-2 have similar electrostatic potentials and dispersion interactions between metal and N5 ring. The comparable intramolecular interactions of M-1 and M-2 lead to similar N5 ring stability. Compared to M-1 and M-2, M-3 has a more negative charge on N5 ring and stronger dispersion interaction. The stronger intramolecular interactions of M-3 result in the higher N5 ring stability. For M-1 and M-2, different metals have slight affects on N5 ring stability. For M-3, N5 ring stability decreases in the order of Li > Na > K. The substituted metal lowers E(g) of PhN5.