DFT studies on the structures and stabilities of N5 +-containing salts

Abstract

Density functional theory (DFT) methods have been applied to study the properties of series of N 5 ? salts. The thermal stabilities of the crystals are evaluated based on the reaction enthalpy (DH) and free energy change (DG) of the salts when they dissociate into neutral products. The energy outputs of salts in explosion indicate that all N 5 ? salts yield large energy except for N 5 SbF 6 and N 5 Sb 2 F 11 . Considering the released energy and thermal stability, (N 5 ) 2 SnF 6 , N 5 PF 6 , N 5 BF 4 , and N 5 SO 3 F may be potential candidates of very energetic explosives.

Towards understanding the stability of the N5+-containing salts: the role of counterions

“…The structure of N 5 SbF 6 (see structure 2 in Fig. 1) was in good agreement with the reported data, 23 which proved that our employed method was reliable. The obtained structures of N 5 +containing salts 1 to 11 are depicted in Fig.…”

“…Most published papers on N 5 + -containing salts focused on their synthesis and properties, whereas there seems to have been limited research on the mechanism of their thermodynamic stability. 22,23 Questions arise, such as why N 5 SbF 6 has quite high thermal stability. In order to gain insight into the role of the central Sb atom as well as of the ligand F atoms in SbF 6 À , other N 5 + M À salts (M ¼ Sb(OH) 6 , SbF 2 (OH) 4 , BF 4 , B(CF 3 ) 4 , AlF 4 , AlF 6 , AsF 6 , and PF 6 ) (Scheme 1) have been selected for a comparative study.…”

Multiwfn: A multifunctional wavefunction analyzer

“…If real space function is chosen as electron density, then the P def (r) is often referred as deformation density, which is very useful in bonding nature analysis. [37,38] The topology of electron density…”

Hydrogen‐Bonding Interactions and Properties of Energetic Nitroamino[1,3,5]triazine‐Based Guanidinium Salts: DFT‐D and QTAIM Studies

“…This method has been applied successfully to high-nitrogen-content compounds. [43,[46][47][48][49] The heat of formation of salt M p X q (D f H8 solid ) is another important thermochemical property and is usually taken as an indicator of the "energy content" of energetic explosives. Based on a Born-Haber energy cycle, [9,10] D f H8 solid can be simplified by Equation (5):…”