Theoretical Investigation of Energetic Salts with Pentazolate Anion.

Energetic salts based on pentazolate anion (-N) have attracted much attention due to their high nitrogen contents. However, it is an enormous challenge to efficiently screen out an appropriate cation that can match well with -N. The vertical electron affinity () of the cations and vertical ionization potential () of the anions for 135 energetic salts and some -N salts were calculated by the density functional theory (DFT). The magnitudes of and , and their matchability were analyzed. The results based on the calculations at the B3LYP/6-311++G(d,p) and B3LYP/aug-cc-pVTZ levels indicate that there is an excellent compatibility between -N and cation when the difference between the of cation and the of -N anion is -2.8 to -1.0 eV. The densities of the salts were predicted by the DFT method. Relationship between the calculated density and the experimental density was established as = 1.111 - 0.06067 with a correlation coefficient of 0.905. This regression equation could be in turn used to calibrate the calculated density of the -N energetic salts accurately. This work provides a favorable way to explore the energetic salts with excellent performance based on -N.