Comparative Theoretical Studies on Energetic Ionic Salts Composed of Heterocycle-Functionalized Nitraminofurazanate-Based Anions and Triaminoguanidinium Cation

Abstract

Density functional theory and volume-based thermodynamics calculations have been performed to study the crystal densities, heats of formation (HOFs), energetic properties, thermodynamics of formation, and impact sensitivity for the salts composed of heterocycle-functionalized nitraminofurazanate-based anions and triaminoguanidinium cation. The results show that the triaminoguanidinium nitraminofurazanate-based salts have high densities and positive HOFs. The substitution of the oxygen-containing substituent (−NO2 or −C­(NO2)3) is helpful for enhancing the densities and detonation properties of the nitraminofurazanate-based salts, and the substitution of −C­(NO2)3 exhibits the best performance. Incorporating the conjugated bridge −NN– or −NN–NN– into the heterocycle-functionalized nitraminofurazanate-based salts is favorable for improving the density and detonation properties of its salt. The tetrazole-functionalized salts exhibit the best detonation properties among the three salt series. The calculated h 50 values suggest that the introduction of the bridge −NH– or −NH–NH– decreases the sensitivities of the heterocycle-functionalized nitraminofurazanate-based salts.

Theoretical Study of High-nitrogen Salts Composed of Ammonium Cations and Pyrazole-derived Anions

“…The Gaussian 09 program package was used to perform the calculations [24]. The geometries of all pyrazole-derived salts were fully optimized at the DFT (B3LYP) level with 6-31++G(d) basis set which was successfully applied to calculate the properties of energetic salts [25][26]. Since density is the key parameter to predict energetic performance, some approaches have been evolved in order to predict the crystal density more accurately [27][28][29].…”

Synthesis and Characterization of New Melt‐cast Energetic Salts: Dipotassium and Diaminoguanidinium N,N′‐Dinitro‐N,N′‐Bis(3‐dinitromethyl‐furazanate‐4‐yl)methylenediamine

“…The geometric optimization, frequency analysis and singlepoint-energy calculation of anion and cations of 4 and 5 were accomplished at the M06-2X/6-311 + G(d,p) level by using Born-Haber Cycle [26,27]. The gaseous heat of formation of small species was computed based on the atomization energies were obtained by employing the CBS-4 M method [28,29] or experimental values directly adopted from the NIST Chemistry Webbook [30] and gaseous phase heat of formation was computed via isodesmic reactions.…”

Theoretical Investigation of Energetic Salts with Pentazolate Anion

“…The structures of energetic salts (Tables S2-S154) were optimized by density functional theory (DFT) by B3LYP method with 6-311++G(d,p) and aug-cc-pVTZ basis sets [25,26]. On this basis, PCM solvation model was used to optimize the geometries of salts in aqueous phase since the cyclo-N 5 − salts and most other energetic salts are crystalized in water.…”