A DFT-D study on the stability and intramolecular interactions of the salts of 1,2,3-and 1,2,4-triazoles

作者：Zhang Xueli; Gong Xuedong^*

来源：Canadian Journal of Chemistry, 2014, 92(11): 1111-1117.

DOI：10.1139/cjc-2014-0343

• 1
• 2
• 3-and 1
• 2
• 4-triazoles
• stability
• hydrogen bonds
• intramolecular interaction
• quantum chemistry

Nitrogen-rich 1,2,4-triazole (1) and 1,2,3-triazole (2) react as bases with the oxygen-rich acids HNO3 (a), HN(NO2)(2) (b), and HClO4 (c) to produce energetic salts (1a, 1b, and 1c and 2a, 2b, and 2c, respectively) potentially applicable to composite explosives and propellants. In this study, these salts were studied with the dispersion-corrected density functional theory. For the isomers such as 1a and 2a, the more negative Delta(r)G(m) of the formation reaction leads to a higher thermally stable salt. The ability to form intramolecular hydrogen bonds predicted with the quantum theory of atoms in molecules has the order of 2 > 1. Different hydrogen bonds result in different second-order perturbation energies, redshifts in IR, and electron density differences. The charge transfer, binding energy, dispersion energy, lattice energy, and energy gap between frontier orbits in the salts of 1 are larger than those of 2, which is helpful for stabilizing the former, and 1 is more obviously stabilized than 2 by formation of salts. Different conformations of 1 and 2 hardly affect the frontier orbital distributions. Base 1 is a more preferred base than 2 to form salts.

• 出版日期2014-11
• 单位南京理工大学