Towards understanding the stability of the N<sub>5</sub><sup>+</sup>-containing salts: the role of counterions

Yu, Yi; Li, Yuchuan; Chen, Ji‐feng; Sun, Chia‐Chung; Li, Jinshan; Fan, Guijuan; Pang, Siping; Zhang, Rubo

doi:10.1039/c5ra16304h

Cited by 9 publications

(4 citation statements)

References 26 publications

(23 reference statements)

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“…For N 5 + salts (A to J), all the anions are located inside the V-shape of the N 5 + . These spatial relative configurations are consistent with previous studies ( Wang et al, 2011 ; Lian et al, 2012 ; Yu et al, 2015 ). The reason for this spatial distribution may be due to the electrostatic potential distribution on the surface of the N 5 + .…”

Section: Resultssupporting

confidence: 93%

The ionic salts with super oxidizing ions O2+ and N5+: Potential candidates for high-energy oxidants

Yang

Li²,

Li³

et al. 2022

Front. Chem.

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As an important component of energetic materials, high-energy oxidant is one of the key materials to improve their energy. The oxidizability of oxidant directly determines the intensity of combustion or explosion reaction. It is generally believed that when the nature of reductant is certain, the stronger the oxidizability, the more intense the reaction. Dioxygenyl cation (O2+) and pentazenium cation (N5+) are two kinds of super oxidizing ions, which oxidizability are comparable to that of fluorine. A series of high energetic ionic salts with O2+, N5+ and various anions as active components are designed, and the results show that: 1) Most ionic salts have appropriate thermodynamic stability, high density (up to 2.201 g/cm3), high enthalpy of formation (up to 1863.234 kJ/mol) and excellent detonation properties (up to 10.83 km/s, 45.9 GPa); 2) The detonation velocity value of O2 (nitrotetrazole-N-oxides) and O2B(N3)4 exceed 10.0 km/s, and the detonation pressure exceed 45.0 GPa because of the O2+ salts have higher crystal density (g/cm3) and oxygen balance than that of N5+salts; 3) With a higher nitrogen content than O2+, the N5+ salts have higher enthalpy of formation, which exceed 330 kJ/mol than that of O2+ salts; 4) The linear spatial structure of N5+ leads the salts to reduce their density. Encouragingly, this study proves that these super oxidizing ions have the potential to become high-energy oxidants, which could be a theoretical reference for the design of new high energetic materials.

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Section: Resultssupporting

confidence: 93%

The ionic salts with super oxidizing ions O2+ and N5+: Potential candidates for high-energy oxidants

Yang

Li²,

Li³

et al. 2022

Front. Chem.

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“…Thus, no known crystal structure of this compound exists. Attempts to clarify the thermal stability of salts can be found in the work of Yu 11 , where the relative stability of the salts is attributed to the role played by the central atom of the counter anion (e.g. As, Sb.…”

Section: Introductionmentioning

confidence: 99%

Predicting the crystal structure of $$\hbox {N}_5\hbox {AsF}_6$$ high energy density material using ab initio evolutionary algorithms

Benchafia

Wang

Iqbal

et al. 2021

Sci Rep

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Abstract$$\hbox {N}_5\hbox {AsF}_6$$ N 5 AsF 6 is the first successfully synthesized salt that has a polymeric nitrogen moeity ($$\hbox {N}_5^+$$ N 5 + ). Although 12 other $$\hbox {N}_5^+$$ N 5 + salts followed, with $$\hbox {N}_5\hbox {SbF}_6$$ N 5 SbF 6 and $$\hbox {N}_5\hbox {Sb}_2\hbox {F}_{11}$$ N 5 Sb 2 F 11 being the most stable, the crystal structure of $$\hbox {N}_5\hbox {AsF}_6$$ N 5 AsF 6 remains unknown. Currently, it is impossible to experimentally determine the structures of $$\hbox {N}_5\hbox {AsF}_6$$ N 5 AsF 6 due to its marginal stability and explosive nature. Here, following an ab initio evolutionary prediction and using only the stoichiometry of $$\hbox {N}_5\hbox {AsF}_6$$ N 5 AsF 6 as a starting point, we were able to reveal the crystal structure of this high energy density material (HEDM). The $$\hbox {C}_{2V}$$ C 2 V symmetry of the $$\hbox {N}_5^+$$ N 5 + cation, as suggested from earlier investigations, is confirmed to be the symmetry adopted by this polymeric nitrogen within the crystal. This result gave full confidence in the validity of this crystal prediction approach. While stability of the $$\hbox {N}_5^+$$ N 5 + within the crystal is found to be driven by electronic considerations, the marginal stability of this HEDM is found to be related to a partial softening of its phonon modes.

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“…This is due to their unique and yet unknown chemistry, and due to their tendency to decompose exothermically into N 2 molecules, which implies a potential usage as high-energy-density materials (HEDM). − Efforts in this field are directed mainly at searching for new polynitrogen molecules and materials, − as well as finding methods for stabilizing them. − Although remarkable progress was made, the field is still in its infancy, as new and surprising results concerning the existence of new and stable polynitrogen species appear frequently in the literature. Consequently, there is a growing motivation for computational work aimed at understanding the molecular level structure of these materials, as well as predicting new materials from first principles. − …”

Section: Introductionmentioning

confidence: 99%

Structures, Stability, and Decomposition Dynamics of the Polynitrogen Molecule N₅⁺B(N₃)₄^– and Its Dimer [N₅⁺]₂[B(N₃)₄^–]₂

et al. 2019

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There is much current interest in materials that are made entirely or mostly of nitrogen atoms. Such materials, polynitrogens, may reveal new aspects of nitrogen chemistry, and are believed to provide a possible basis for novel energetic substances. An interesting family of such materials, in which the N 5 + group appears as a cation, was prepared by K. O. Christe and co-workers. Little is known as yet on the microscopic properties of these materials. In this paper, we report theoretical calculations to predict the structure, energetic stability and decomposition dynamics of the polynitrogen molecule N 5 + B(N 3 ) 4 − , the building block of a solid prepared by Christe, and of the dimer of this molecule. The structures are computed at the B3LYP-D3 level of DFT. ab initio molecular dynamics simulations are used to explore the thermal stability of the species and the decomposition mechanism. It is found that the N 5 + B(N 3 ) 4− ion-pair decomposes on a picosecond time scale at T = 200 K, with an ultrafast release of four N 2 molecules, which is very exothermic. The species B(N 3 ) 3 is a product. The dimer is considerably more stable. Sensitivity of the process to temperature and to an applied force is reported. Possible applications of this material are briefly discussed.

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

Abstract: The role of counterions of N5+-containing salts in stabilizing N5+ cations was studied by means of density functional theory.

Cited by 9 publications

References 26 publications

The ionic salts with super oxidizing ions O2+ and N5+: Potential candidates for high-energy oxidants

The ionic salts with super oxidizing ions O2+ and N5+: Potential candidates for high-energy oxidants

Predicting the crystal structure of $$\hbox {N}_5\hbox {AsF}_6$$ high energy density material using ab initio evolutionary algorithms

Structures, Stability, and Decomposition Dynamics of the Polynitrogen Molecule N₅⁺B(N₃)₄^– and Its Dimer [N₅⁺]₂[B(N₃)₄^–]₂

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

Abstract: The role of counterions of N5+-containing salts in stabilizing N5+ cations was studied by means of density functional theory.

Cited by 9 publications

References 26 publications

The ionic salts with super oxidizing ions O2+ and N5+: Potential candidates for high-energy oxidants

The ionic salts with super oxidizing ions O2+ and N5+: Potential candidates for high-energy oxidants

Predicting the crystal structure of $$\hbox {N}_5\hbox {AsF}_6$$ high energy density material using ab initio evolutionary algorithms

Structures, Stability, and Decomposition Dynamics of the Polynitrogen Molecule N5+B(N3)4– and Its Dimer [N5+]2[B(N3)4–]2

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

Structures, Stability, and Decomposition Dynamics of the Polynitrogen Molecule N₅⁺B(N₃)₄^– and Its Dimer [N₅⁺]₂[B(N₃)₄^–]₂