A DFT-D study on the stability and intramolecular interactions of the energetic salts of 3,6-dihydrazido-1,2,4,5-tetrazine

Abstract

Structures of the salts I–IV formed by 3,6-dihydrazido-1,2,4,5-tetrazine with HNO3, HN(NO2)2, HClO4, and HC(NO2)3, respectively, were studied using dispersion-corrected density functional theory. The intramolecular hydrogen bond energies of I–IV were estimated using the quantum theory of atoms in molecules. The total hydrogen bond energies (EH,tot) have the order of I (65.60 kcal/mol) > II (46.24 kcal/mol) > III (39.13 kcal/mol) > IV (19.68 kcal/mol). In addition, the charge transfer (q), binding energy (Eb), lattice energy (HL), dispersion energy (Edis), and second-order perturbation energy (E2) were evaluated for studying the intramolecular interactions between the cation and anion. Linear relationships exist between any two of EH,tot, qtot, Eb, and E2,tot. HLs have the same variation trend as h50s (characteristic height) and may be used as the indicator of impact sensitivity. The HOMOs and LUMOs of I–IV are derived from the HOMOs of the isolated anions and the LUMOs of the isolated cations, respectively. Ultraviolet spectra of I–IV have the strongest absorptions at around 442, 445, 427, and 587 nm, respectively. The excitations HOMO→LUMO to HOMO–7→LUMO play important roles in the first three excited states.