Layered single-bonded nonmolecular phase of nitrogen from first-principles simulation

Zahariev, Federico; Hu, Amanda; Hooper, James; Zhang, F.; Woo, Tom K.

doi:10.1103/physrevb.72.214108

Cited by 92 publications

(67 citation statements)

References 41 publications

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“…1 Recently, there have been many studies on the thermodynamic stability of other polymeric crystalline phases of nitrogen, with some possessing lower enthalpy than cg-N at higher pressures, though none have been observed experimentally. [8][9][10][11][12][13][14][15][16][17] Previous shock-wave experiments have shown that molecular liquid nitrogen undergoes a continuous transformation to a conducting atomic liquid at high-P and T . [18][19][20] Subsequent first-principles calculations 21,22 also reported molecular dissociation and metallization in good agreement with experiment.…”

Section: Introductionmentioning

confidence: 99%

Electronic and structural properties of dense liquid and amorphous nitrogen

Boates

Bonev

2011

Phys. Rev. B

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We present first-principles calculations of the structural and electronic properties of liquid nitrogen in the pressure-temperature range of 0-200 GPa and 2000-6000 K. Upon polymerization, the liquid becomes metallic, similar to what has been reported for the higher-temperature atomic fluid. An explanation of the electronic properties of the transformed liquids and the differences with the electronic properties of insulating solid cubic-gauche nitrogen is given based on the structure and bonding character of these phases. The mechanism responsible for charge transport in polymeric nitrogen systems is examined in order to understand the semi-conducting nature of low-temperature amorphous nitrogen.

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Section: Introductionmentioning

confidence: 99%

Electronic and structural properties of dense liquid and amorphous nitrogen

Boates

Bonev

2011

Phys. Rev. B

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“…3 of Ref. 30 ). Although many new forms of nitrogen have been predicted in the last years, no ab initio dynamical simulations have been performed to study the process of the molecular-nonmolecular transition -except for one study using classical force field 65 and an investigation of an opposite process of cg-N shockinduced depolymerization studied by first-principles dynamic simulations 66,67 .…”

mentioning

confidence: 88%

“…This insulating phase yields unusual structure with I2 1 3 symmetry, which is composed of fused N 10 rings connected in a way that maximizes the number of energetically favorable gauche dihedral angles (of lp-N-N-lp with lp being the electron lone-pair), which minimize the effect of mutual lp repulsion 5,30 . In this conformation all N atoms are 3c and single-bonded and local N-N-N angles are nearly tetrahedral -cg-N may be therefore viewed within the sp 3 -hybridization scheme with three out of five valence electrons occupying three single-bond orbitals and remaining two accommodating one lone-pair 31 .…”

Section: Introductionmentioning

confidence: 99%

“…More extended phases include fully single-bonded, yet layered forms of black phosphorus (BP) and α-arsenic (A7) composed of fused N 6 rings in chair conformation 5 . Other similar phases with N 6 rings in boat conformation include layered boat (LB) structure with P 2 1 /m symmetry 30 and P nma zigzag sheet (ZS) phase 4142 . By a systematic searching method 26 new metastable phases of nitrogen were discovered 43 demonstrating that a vast number of various structures are in fact feasible for element 7.…”

Section: Introductionmentioning

confidence: 99%

“…In this paper, we primarily focus on resolving the last problem. In the work of Zahariev et al 30 , it was suggested that transformations to layered structures might proceed via zig-zag chain geometry pattern, but it was also pointed out that trans-cis chains might be involved instead, as far as many predicted polymeric forms of N can be viewed as different connections of either zig-zag, or, alternatively, trans-cis chains -e.g. BP, A7, LB or ZS (see Fig.…”

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Transformation pathways in high-pressure solid nitrogen: From molecular N2 to polymeric cg-N

Plašienka

Martoňák

2015

The Journal of Chemical Physics

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The transformation pathway in high-pressure solid nitrogen from N 2 molecular state to polymeric cg-N phase was investigated by means of ab initio molecular dynamics and metadynamics simulations. In our study, we observed a transformation mechanism starting from molecular Immm phase that initiated with formation of trans-cis chains. These chains further connected within layers and formed a chain-planar state, which we describe as a mixture of two crystalline structures -trans-cis chain phase and planar phase, both with P nma symmetry. This mixed state appeared in molecular dynamics performed at 120 GPa and 1500 K and in the metadynamics run at 110 GPa and 1500 K, where the chains continued to reorganize further and eventually formed cg-N. During separate simulations, we also found two new phases -molecular P 2 1 /c and two-threecoordinated chain-like Cm. The transformation mechanism heading towards cg-N can be characterized as a progressive polymerization process passing through several intermediate states of variously connected transcis chains. In the final stage of the transformation chains in the layered form rearrange collectively and develop new intraplanar as well as interplanar bonds leading to the geometry of cg-N. Chains with alternating trans and cis conformation were found to be the key entity -structural pattern governing the dynamics of the simulated molecular-polymeric transformation in compressed nitrogen.

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Novel All‐Nitrogen Molecular Crystals of Aromatic N₁₀

et al. 2020

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Nitrogen has unique bonding ability to form single, double, and triple bonds, similar to that of carbon. However, a molecular crystal formed by an aromatic polynitrogen similar to a carbon system has not been found yet. Herein, a new form of stable all‐nitrogen molecular crystals consisting of only bispentazole N10 molecules with exceedingly high energy density is predicted. The crystal structures and the conformation of N10 molecules are strongly correlated, both depending on the applied external pressure. These molecular crystals can be recovered upon the release of the pressure. The first‐principles molecular dynamics simulations reveal that these all‐nitrogen materials decompose at temperatures much higher than room temperature. The decompositions always start from breaking off N2 molecules from the nitrogen ring and can release a large amount of energy. These new polynitrogens are aromatic and are more stable than all the other polynitrogen crystals reported previously, providing a new green strategy to get all‐nitrogen, nonpolluting high energy density materials without introducing any metal or other guest stabilizer.

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Layered single-bonded nonmolecular phase of nitrogen from first-principles simulation

Cited by 92 publications

References 41 publications

Electronic and structural properties of dense liquid and amorphous nitrogen

Electronic and structural properties of dense liquid and amorphous nitrogen

Transformation pathways in high-pressure solid nitrogen: From molecular N2 to polymeric cg-N

Novel All‐Nitrogen Molecular Crystals of Aromatic N₁₀

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Layered single-bonded nonmolecular phase of nitrogen from first-principles simulation

Cited by 92 publications

References 41 publications

Electronic and structural properties of dense liquid and amorphous nitrogen

Electronic and structural properties of dense liquid and amorphous nitrogen

Transformation pathways in high-pressure solid nitrogen: From molecular N2 to polymeric cg-N

Novel All‐Nitrogen Molecular Crystals of Aromatic N10

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Novel All‐Nitrogen Molecular Crystals of Aromatic N₁₀