Stabilization of pentazolate anions in the high-pressure compounds Na2N5and NaN5and in the sodium pentazolate framework NaN5·N2

Bykov, Maxim; Bykova, Elena; Chariton, Stella; Prakapenka, Vitali B.; Batyrev, Iskander G.; Mahmood, Mohammad F.; Goncharov, Alexander F.

doi:10.1039/d1dt00722j

Cited by 26 publications

(42 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…High pressure investigations greatly expanded on these results, exhibiting the formation of polynitrogen species ([N4] 4-, 3 [N5 -], [4][5][6] [ ] , 3,7,8 and N-frameworks 3,[9][10][11] ).…”

Section: Introductionmentioning

confidence: 99%

High-pressure Na3(N2)4, Ca3(

Laniel

Winkler

Fedotenko

et al. 2022

Phys. Rev. Materials

Self Cite

View full text Add to dashboard Cite

Charged nitrogen dimers [N2]xare ubiquitous in high-pressure binary metal-nitrogen systems.They are known to possess integer formal charges x varying from one through four. Here, we present the investigation of the binary alkali-and alkaline earth metal-nitrogen systems, Na-N, Ca-N, Sr-N, Ba-N to 70 GPa. We report on compounds- Na3(N2)4, Ca3(N2)4, Sr3(N2)4, and Ba(N2)3-featuring [N2] xunits with paradigm-breaking non-integer charges, x = 0.67, 0.75 and 1.5. The metallic nature of all four compounds is deduced from ab initio calculations. The conduction electrons occupy the π* antibonding orbitals of the [N2] xdimers that results in anion-driven metallicity. Delocalization of these electrons over the π* antibonding states enables the non-integer electron count of the dinitrogen species.Anion-driven metallicity is expected to be found among a variety of compounds with homoatomic anions (e.g., polynitrides, carbides, and oxides), with the conduction electrons playing a decisive role in their properties.

show abstract

Section: Introductionmentioning

confidence: 99%

High-pressure Na3(N2)4, Ca3(

Laniel

Winkler

Fedotenko

et al. 2022

Phys. Rev. Materials

Self Cite

View full text Add to dashboard Cite

show abstract

“…Whereas a significant number of studies on binary metal‐nitrogen compounds of alkali, alkaline earth, and transition metal elements under high pressure have been conducted, [1–7, 9–29] the high‐pressure chemistry and physical properties of rare earth metal nitrides are almost unknown. Until recently, in the yttrium‐nitrogen system, only one binary Y−N compound was known: cubic yttrium nitride YN with the rock salt structure [39] .…”

Section: Figurementioning

confidence: 99%

“…À rings, [18][19][20] hexazine N 6 rings, [21][22][23] and different polynitrogen chains [17,[24][25][26][27][28][29] have been synthesized, and an even greater variety of nitrogen species is expected to form under high-pressure conditions according to theoretical calculations. [30][31][32][33][34][35][36][37] Such a diversity of nitrogen species can suggest that the scale of nitrogen chemistry under high pressure may be close to the scale of the rich carbon chemistry at ambient pressure.…”

mentioning

confidence: 99%

Anionic N₁₈ Macrocycles and a Polynitrogen Double Helix in Novel Yttrium Polynitrides YN₆ and Y₂N₁₁ at 100 GPa

et al. 2022

View full text Add to dashboard Cite

Two novel yttrium nitrides, YN6 and Y2N11, were synthesized by direct reaction between yttrium and nitrogen at 100 GPa and 3000 K in a laser‐heated diamond anvil cell. High‐pressure synchrotron single‐crystal X‐ray diffraction revealed that the crystal structures of YN6 and Y2N11 feature a unique organization of nitrogen atoms—a previously unknown anionic N18 macrocycle and a polynitrogen double helix, respectively. Density functional theory calculations, confirming the dynamical stability of the YN6 and Y2N11 compounds, show an anion‐driven metallicity, explaining the unusual bond orders in the polynitrogen units. As the charge state of the polynitrogen double helix in Y2N11 is different from that previously found in Hf2N11 and because N18 macrocycles have never been predicted or observed, their discovery significantly extends the chemistry of polynitrides.

show abstract

“…The C2/m-CdN 6 and C2/m-HeN 22 with respectively highenergy-density values of 3.82 kJ/g and 10.44 kJ/g may be quenchable to ambient pressure. In the experiment, the cyclo-N 5 ring in LiN 5 , NaN 5 and CsN 5 compounds are synthesized at 45, 52 and 65 GPa, respectively [56][57][58]. The CsN 5 and LiN 5 can be quenched down to 18 GPa and ambient pressure, respectively.…”

Section: Introductionmentioning

confidence: 99%

The New High-Pressure Phases of Nitrogen-Rich Ag–N Compounds

Liu

Yao

et al. 2022

Materials

View full text Add to dashboard Cite

The high-pressure phase diagram of Ag–N compounds is enriched by proposing three stable high-pressure phases (P4/mmm-AgN2, P1-AgN7 and P-1-AgN7) and two metastable high-pressure phases (P-1-AgN4 and P-1-AgN8). The novel N7 rings and N20 rings are firstly found in the folded layer structure of P-1-AgN7. The electronic structure properties of predicted five structures are studied by the calculations of the band structure and DOS. The analyses of ELF and Bader charge show that the strong N–N covalent bond interaction and the weak Ag–N ionic bond interaction constitute the stable mechanism of Ag–N compounds. The charge transfer between the Ag and N atoms plays an important role for the structural stability. Moreover, the P-1-AgN7 and P-1-AgN8 with the high-energy density and excellent detonation properties are potential candidates for new high-energy density species.

show abstract

Stabilization of pentazolate anions in the high-pressure compounds Na₂N₅and NaN₅and in the sodium pentazolate framework NaN₅·N₂

Abstract: Synthesis and characterization of nitrogen-rich materials is important for the design of novel high energy density materials due to extremely energetic low-order nitrogen-nitrogen bonds. The balance between energy output and...

Cited by 26 publications

References 51 publications

High-pressure Na3(N2)4, Ca3(

High-pressure Na3(N2)4, Ca3(

Anionic N₁₈ Macrocycles and a Polynitrogen Double Helix in Novel Yttrium Polynitrides YN₆ and Y₂N₁₁ at 100 GPa

The New High-Pressure Phases of Nitrogen-Rich Ag–N Compounds

Contact Info

Product

Resources

About

Stabilization of pentazolate anions in the high-pressure compounds Na2N5and NaN5and in the sodium pentazolate framework NaN5·N2

Abstract: Synthesis and characterization of nitrogen-rich materials is important for the design of novel high energy density materials due to extremely energetic low-order nitrogen-nitrogen bonds. The balance between energy output and...

Cited by 26 publications

References 51 publications

High-pressure Na3(N2)4, Ca3(

High-pressure Na3(N2)4, Ca3(

Anionic N18 Macrocycles and a Polynitrogen Double Helix in Novel Yttrium Polynitrides YN6 and Y2N11 at 100 GPa

The New High-Pressure Phases of Nitrogen-Rich Ag–N Compounds

Contact Info

Product

Resources

About

Stabilization of pentazolate anions in the high-pressure compounds Na₂N₅and NaN₅and in the sodium pentazolate framework NaN₅·N₂

Anionic N₁₈ Macrocycles and a Polynitrogen Double Helix in Novel Yttrium Polynitrides YN₆ and Y₂N₁₁ at 100 GPa