Towards improving the characteristics of high-energy pyrazines and their N-oxides.

Context: Based on the methods of quantum chemistry and atom–atom potentials, the molecular and crystal structure of a number of high-energy pyrazines was modeled: unsubstituted diazines, as well as fully nitrated 1,4-diazabenzenes, their oxides and polymorphs. The enthalpies of formation, densities of molecular crystals, and some performance characteristics of these compounds were determined. The parameters of decomposition of substances were estimated. It has been established that tetranitropyrazine-1,4-dioxide has maximum energy content and excellent performance characteristics, which determine the prospects for using this compound as a high-energy one in the considered series of compounds. Methods: In this work, DFT calculations were conducted through the software Gaussian 09 using B3LYP functional with basis set aug-cc-PVDZ and the Grimme dispersion correction D2. For crystal structure optimization, the atom–atom potential methods with PMC program (Packing of Molecules in Crystal) were used. Charges for molecular electrostatic potential were fitted by FitMEP and enthalpies of formation in gas phase were assessed by G3B3. [ABSTRACT FROM AUTHOR]