Density Functional Theoretical Study on Intermolecular Interactions of 3,6-Dihydrazino-1,2,4,5-tetrazine Dimers

Abstract

Seven fully optimized geometries of 3,6-dihydrazino-1,2,4,5-tetrazine (DHT) dimers have been obtained with density functional theory (DFT) method at the B3LYP/<TEX>$6-311++G^{**}$</TEX> level. The intermolecular interaction energy was calculated with zero point energy (ZPE) correction and basis set superposition error (BSSE) correction. The greatest corrected intermolecular interaction energy of the dimers is <TEX>$-23.69\;kJ{\cdot}mol^{-1}$</TEX>. Natural bond orbital (NBO) analysis is performed to reveal the origin of the interaction. Based on the vibrational analysis, the changes of thermodynamic properties from the monomers to dimer with the temperature ranging from 200.0 K to 800.0 K have been obtained using the statistical thermodynamic method. It was found that the hydrogen bonds dominantly contribute to the dimers, while the binding energies are not only determined by hydrogen bonding. The dimerization process can not occur spontaneously at given temperatures.