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A New Allotrope of Nitrogen as High-

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Arnab Majumdar
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A New Allotrope of Nitrogen as High-Energy Density Material

Michael J. Greschner,†,‡ Meng Zhang,*,§ Arnab Majumdar,† Hanyu Liu,∥ Feng Peng,⊥,# John S. Tse,†
and Yansun Yao*,†,‡
†
Department of Physics and Engineering Physics, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5E2, Canada
‡
Canadian Light Source, Saskatoon, Saskatchewan S7N 2V3, Canada
§
Department of Physics, East China University of Science and Technology, Shanghai 200237, China
∥
Geophysical Laboratory, Carnegie Institution of Washington, NW, Washington, D.C. 20015, United States
⊥
College of Physics and Electronic Information, Luoyang Normal University, Luoyang 471022, China
#
Beijing Computational Science Research Center, Beijing 10084, China
*
S Supporting Information

ABSTRACT: A new allotrope of nitrogen in which the atoms are connected to form a
novel N6 molecule is predicted to exist at ambient conditions. The N6 molecule is a
charge-transfer complex with an open-chain structure containing both single and triple
bonds. The charge transfer induces ionic characteristics in the intermolecular
interactions and leads to a much higher cohesive energy for the predicted crystal
compared to solid N2. The N6 solid is also more stable than a previously reported
polymeric solid of nitrogen. Because of the kinetic stability of the molecules and strong
intermolecular interactions, the N6 crystal is shown by metadynamics simulations to be
dynamically stable around room temperature and to only dissociate to N2 molecules above 700 K. The N6 crystal can likely be
synthesized under high-pressure high-temperature conditions, and the considerable metastability may allow for an ambient-
pressure recovery of the crystal. Because of the large energy difference between the single and triple bonds, the dissociation of the
N6 crystal is expected to release a large amount of energy, placing it among the most efficient energy materials known today.

■ INTRODUCTION Theoretical predictions9−14 have been demonstrated to be

Allotropic modifications of nitrogen, that is, compounds
consisting of endothermic nitrogen molecules, have been
actively investigated as high-energy-density materials
(HEDM). Under ambient conditions, nitrogen exists as a
diatomic N2 form with a triple bond. This bonding is
recognized as the strongest in nature, making N2 chemically
inert. At cryogenic conditions, N2 crystallizes into a solid in
which the molecules are held together by van der Waals (vdW)
forces. Allotropic modification of nitrogen is achieved by
transforming N2 into single- or double-bonded metastable
forms, such as polynitrogen molecules or polymeric crystals.1−5
Because of the large energy difference between the single (∼40
kcal mol−1) and triple bonds (∼225 kcal mol−1), nitrogen
allotropes are efficient energy carriers, which, if metastable at
ambient conditions, would be placed among the most powerful
HEDMs known today. The decomposition of nitrogen
allotropes is environmentally friendly, producing only nontoxic
N2. In 1992, Mailhiot et al. made a ground-breaking
prediction,6 that a solely single-bonded phase of nitrogen
(the “cubic gauche” (cg) phase) could be thermodynamically
stable under high pressure. Remarkably, after overcoming
substantial experimental difficulties, the cg phase was
successfully synthesized in 2004 via high-pressure (>120
GPa) high-temperature (>2500 K) techniques.7 Along with
the cg phase, amorphous nitrogen was also synthesized, which
contains nonmolecular nitrogen clusters.8
very successful in leading to the discovery of new nitrogen
allotropes. In recent years, several hypothetical structures have
made their real-world appearance in laboratory, including the
N3 and N4 molecules,1 N5 ions,4,5 as well as the polymeric
crystal.7 In a recent study, Hirshberg et al.15 predicted the
existence of a molecular crystal of nitrogen consisting of novel
N8 molecules. This solid contains two different isomers of N8,
where the two N4 units are connected in either cis (Z) or trans
(E) configuration with respect to the central double bond. This
crystal was predicted to be metastable at ambient conditions
and to have a large energy content (∼260 kcal mol−1), which is
superior to many modern HEDMs. The N8 crystal was
suggested to be formed from a crystal composed of the N4
molecules, while the synthesis of this precursor is still ongoing.
This therefore motivated us to explore the possibility of finding
crystals with polynitrogen molecules that may be directly
formed from N2. In this study we focus on the N6 molecules. As
per the Lewis structures, the N6 and N8 molecules have a
similar number of single bonds and therefore have comparable
energy content. As well, it may be possible to form N6
molecules directly from N2. The N2 to N6 transition is
associated with a large energy barrier, which inhibits the
Received: February 18, 2016
Revised: April 13, 2016
Published: April 18, 2016

© 2016 American Chemical Society 2920 DOI: 10.1021/acs.jpca.6b01655

J. Phys. Chem. A 2016, 120, 2920−2925
The Journal of Physical Chemistry A
transition at ambient conditions. The energy barrier may be
overcome by applying external pressure. As shown previously
by molecular dynamics (MD) simulations,16 crystalline N2 (ε-
phase) can be transformed without a barrier to a crystalline
mixture containing N2 and N6 molecules near 60 GPa.
Experimentally, evidence of a cyclic N6 molecule (benzene
analogue) has been observed in an elimination reaction of a
diazido platinum complex at 77 K.17 Different synthetic routes
to N6 isomers18−20 have been theoretically investigated, while
the crystalline phases21 have been experimentally attempted
using the photolysis of compressed sodium azide (NaN3).
Recently, crystals containing ionized N6 molecules were
predicted to form in alkali metal nitrides under high
pressure.22−28 Crystals consisting of neutral N6 molecules,
however, are a relatively new territory yet to be explored, both
theoretically and experimentally.
In the present study, we investigated the possible existence of
crystalline N6 using state-of-the-art first-principles computa-
tional methods. The global minimum geometry of the N6
molecule is identified to have a charge-transfer open chain
structure. Because of the charge disparity of the N6 molecules,
in the solid state, the N6 molecules are stabilized by strong
electrostatic attractions from four nearest-neighbor molecules.
These ionic interactions resulted in a fairly high cohesive energy
(7.09 kcal mol−1) making the crystal structure metastable at
ambient conditions. This is supported by metadynamics
simulations showing that the new allotrope of nitrogen is
dynamically stable around room temperature, and only
dissociates to pure N2 above 700 K. The dissociation is highly
exothermic with a large energy release (estimated as 185 kcal
mol−1). Because of the stability of the N6 molecule and strong
electrostatic interactions in the crystalline environment, the
predicted crystal has considerable kinetic stability and may be
recoverable once it is produced under high pressure.
■ METHODS
The search for the global minimum geometry of the N6
molecule was performed using the swarm-intelligence Crystal
structure Analysis by Particle Swarm Optimization (CALYP-
SO) algorithm.29,30 More than 400 distinct N6 isomers were
generated in the search and fully relaxed using all-electron, spin-
unrestricted relativistic calculations, with the Perdew−Burke−
Ernzerhof (PBE) functional31 and double-numerical basis sets
including d polarization functions implemented in the DMoL3
program.32 After the relaxation, the low-energy isomers were
selected for more refined optimization and vibrational analysis,
using the MP2 calculations with a larger cc-pVDZ basis set and
the Gaussian09 package.33 Crystal structures were constructed
from random distributions of the lowest energy N6 molecules.
Five hundred stacking patterns were generated in unit cells of
arbitrary shapes containing up to four N6 molecules. Crystal
structures were fully optimized using the Vienna Ab initio
Simulation Package (VASP).34 A projector augmented wave
potential35 with the PBE functional and a cutoff energy of 400
eV were used. Phonons were calculated on a 2 × 2 × 2
supercell using the finite displacement method.36 Enthalpy and
electronic structure calculations were performed with the VASP
code. A dense 12 × 12 × 12 k-point grid was used to sample
the Brillouin zone (BZ), which was shown to yield convergence
for total energies within 1 meV atom−1. Metadynamics
simulations37 were performed in supercells with eight N6
molecules with a 2 × 2 × 2 k-point mesh for BZ sampling.
Each metastep consisted of an MD simulation in an NVT
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ensemble using VASP and optPBE-vdW functional38,39 to take
into account the vdW interactions.
■ RESULTS AND DISCUSSION
The N6 Molecule: Diazide or Benzene Analogue?
There have been many theoretical studies40−45 addressing the
stability of the N6 isomers, either regarding it as an open-chain
diazide (e.g., C2h, C2v) or as a benzene analogue (e.g., D6h, D2h,
D2). The swarm-intelligence structure search and vibrational
analysis identified a number of N6 isomers in both categories
(for details see Supporting Information). From this, it appears
that the open chain structures are more energetically favorable
than the ring structures. The diazide C2h geometry was found to
be the global minimum, while the benzene analogue D6h and its
Jahn−Teller variation C2 are at 1.30 and 1.19 eV above,
respectively. This suggests that the triple bonding in open-chain
structures are substantially more favorable than the π bonding
in benzene analogues.
The geometry of the C2h isomer is consistent with a N3−−
N3+ adduct (Figure 1a), which could dissociate into a (N2)3
Figure 1. Structure and electronic structure of the global-minimum N6
molecule. (a) Optimized C2h geometry and (b) dissociation to N2.
Numbers are NBO charges (e−, red) and bond lengths (Å, black),
respectively. (c) The Lewis structure and (d) deformation electron
density. (e, f) Isosurfaces of two HOMOs plotted using the isovalue of
0.01 e− Å−3. All calculations were completed at the MP2/cc-pVDZ
level.
trimer (Figure 1b). Natural bond orbital (NBO) analysis46
reveals that the two identical terminal bonds, N1−N5 and N3−
N6, have strong triple bond character with the bond length of
1.16 Å, which is only slightly longer than the bond length in N2
(1.11 Å). Between the N4 and N2 atoms the bond is a single
bond, with the bond length of 1.46 Å. The bond length for the
two internal bonds, N5−N4 and N2−N3, is 1.26 Å, which is
similar to the bond length in diazene N2H2 (1.25 Å). The NBO
analysis reveals that the N5−N4 and N2−N3 are polar bonds,
with an amount of charge (∼0.2 e−) being transferred from the
N5 (N3) atom to the N4 (N2) atom. The Lewis structure and
Voronoi deformation density of the C2h isomer are shown in
Figure 1c,d. This molecule is stabilized by several resonance
structures, namely, NN+−N−−N−−N+N ↔ NN+N−
N−−N−N+. Molecular orbitals (MO) analysis (Figure 1e,f)
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indicates that the two degenerate highest occupied molecular
orbitals (HOMOs) are derived from the N5−N4 and N2−N3
bonding orbitals, where the π characters are clearly visible
(additional MOs are provided in Supporting Information). In
the N6 molecule the 2pπ orbital has higher energy than the 2pσ
orbital, which differs from the situation of N2, where the two
orbitals have an energy crossover. The absence of the crossover
in the N6 molecule is due to the elongated NN bond length,
which results in a lower bond order for the 2pσ orbital and less
antibonding mixing with the 2sσ orbital. The dissociation of the
N6 molecule involves simultaneous breaking of the N5−N4 and
N2−N3 bonds (Figure 1b), with a calculated energy release of
8.33 eV/N6 at T = 0 K.
The (N6)2 Dimer: Electrostatic Stabilization by Molec-
ular Charge Disparity. In the crystalline environment, N6
molecules are expected to preserve their chemical integrity. The
intermolecular interactions are mainly vdW and electrostatic in
origin. This bonding environment was analyzed on the global-
minimum (N6)2 dimer (Figure 2). In the dimer, the two N6
Figure 2. Structure of the global-minimum (N6)2 dimer. Numbers in
red and black indicate the NBO charges (e−) and N−N distances (Å),
respectively.
molecules are identical and suited in a way that the closest N···
N contact (2.89 Å, less than the sum of two vdW radii)
connects the N3(N5) and N2(N4) atoms of the two molecules.
Figure 3. Structure and energetics of the crystalline nitrogen. (a) Unit cell of the crystalline N6 structure with the C2/m space group. (b) Network of
the intermolecular N···N contacts shown in a slab of N6 molecules in the structure. (c) Calculated enthalpies per atom for different forms of
crystalline nitrogen. The enthalpy of the cg structure is used as the zero-energy reference level.
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Such an arrangement therefore favors attractions between
atoms with the opposite charges, and minimizes repulsions
between lone pairs. Calculated cohesive energy for the (N6)2
dimer is 5.54 kcal mol−1, suggesting strong interactions
between N6 molecules.
The N6 Crystal: Maximized Electrostatic Stabilization.
The lowest-energy crystal structure has a monoclinic unit cell
with the C2/m space group (Figure 3a; see structural
parameters in Supporting Information). The number of nearest
neighbors is maximized in the crystalline phase. In this
structure, the N6 molecules are only slightly distorted from
their gas-phase geometry. The bond lengths for the N1−N5,
N5−N4, and N2−N4 bonds are 1.15, 1.24, and 1.42 Å,
respectively, very close to the gas-phase values. In the C2/m
structure, the N6 molecules are arranged in slabs, while the slabs
are held together by vdW interactions (Figure 3b). Within the
slab, the intermolecular N···N interactions are maximized
through electrostatic attractions from four nearest neighbors,
which results in a cohesive energy of ∼7.09 kcal mol−1
(calculated as the difference between the average energy of a
N6 unit in solid and the energy of a gas-phase N6 at T = 0 K).
The cohesive energy of the N6 solid is substantially higher than
the cohesive energy of the N2 solid (∼1.98 kcal mol−1). The
difference can be attributed to the enhanced intermolecular
interactions due to the charge disparity of the N6 molecules.
Using the energy difference between the N2 and N6 molecules,
and the cohesive energy of the N6 crystal, the energy release in
the dissociation of the N6 crystal to N2 molecules is estimated
to be ∼185 kcal mol−1 (or 61.6 kcal mol−1 per N2) at T = 0 K.
Such a high energy density, if realized, would place the N6
crystal among the best performing high-energy materials known
today.
To examine the energetics of the N6 crystal, the enthalpy of
the C2/m structure was calculated and compared with other
crystalline forms of nitrogen (Figure 3c). The vdW interactions
were taken into account using nonlocal optPBE-vdW density
functional. The calculation was also repeated using semi-
empirical DFT-D2 corrections,47 and the standard PBE
functional (see details in Supporting Information). In the
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J. Phys. Chem. A 2016, 120, 2920−2925
The Journal of Physical Chemistry A
studied pressure range, the most stable crystalline phase is the
one consisting of solely N2 molecules; its overwhelming
stability is owed to the strong NN bonds. At ambient
pressure, the cg phase7 is energetically the least favorable due to
the high energy of the N−N bonds. The nonmolecular
structure that contains extended chains of alternating single and
double bonds16 has lower energy than the cg phase. Both the
N6 crystal and the N8 crystal15 have a mixture of single and
triple bonds, so their enthalpies are comparable. Clearly the
energetic order at ambient pressure is determined by the
stability of the constituent nitrogen forms, but nonmolecular
crystals (cg and extended chain structures) are denser than
molecular ones, and therefore they are favored by virtue of
smaller pV works at high pressure. Most importantly, the N6
crystal is calculated to be more stable than the cg phase below
22 GPa and more stable than the extended chain structure
below 5.2 GPa, so it is the most preferred nonmolecular N2
structure.
The bonding pattern in the N6 crystal was analyzed through
the electron localization function48 (ELF; Figure 4a,b). A σ
Figure 4. Electronic structure of the crystalline N6. (a) Three
dimensional ELF isosurface (value = 0.7) and (b) the ELF contours
drawn in the plane that contains the N6 molecules. “LP” indicates the
lone pairs. (c) Electronic band structure and projected DOS calculated
at ambient pressure.
bond is clearly identified between N4 and N2 atoms as well as
the lone pairs outside the molecule. Between N5(N3) and
N4(N2) the bonding is predominately σ type with admixture of
π bonding. The bonding between N1(N6) and N5(N3) has
both σ and π characters, consistent with a triple bond
description. The band structure and density of states (DOS;
Figure 4c) show that the N6 crystal has an insulating ground
state with a pseudodirect band gap of ∼1.7 eV, approximately at
the energy lower limit for visible light spectrum (Note that the
band gap is likely underestimated in generalized gradient
approximation (GGA)). The projected DOS shows that the
energy bands located around the band gap are characteristic of
the 2pπu (below) and 2pπg* (above) orbitals. Orbitals with s-
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character are located in lower energy regions, in particular,
between −5 and −10 eV, where the 2pσg orbital mixes with
2sσg orbital. Phonon dispersion relations for the N6 crystal were
calculated at ambient pressure (Supporting Information).
Notably, all vibrational modes were found to be positive,
suggesting this crystal is mechanically stable and might be
quench recoverable at ambient pressure. The metastability is
due to the intrinsic stability of the N6 molecule and the nearest-
neighbor electrostatic interactions in the solid phase.
Thermal Effect on the N6 Crystal: Dissociation and
Energy Release. Metadynamics simulations were employed to
provide insight into the thermodynamic behavior of the N6
crystal. Calculations were performed at 1 atm and different
temperatures, namely, 300, 500, 700, 1200, 1500, and 2000 K,
with a simulation time over 40 ps (0.4 ps for each metastep). At
300 K, the crystal was found to be stable, where the thermal
fluctuation of the volume is clear (Figure 5a). The dissociation
of the crystal started at 700 K, and it became more dramatic at
elevated temperatures (Figure 5a,b). At 700 and 1200 K, the
enthalpy evolution in the simulation shows a stepwise path,
where the plateau regions represent progressive dissociations of
the N6 molecules. At 1200 K, plateaus in the enthalpy were
observed at metasteps 5−7, metasteps 8−16, and metasteps
18−29, corresponding to the dissociation of 1/2, 5/8, and 7/8
of N6 molecules in the crystal, respectively, until, eventually,
pure N2 is observed at the 30th metastep (Figure 5c). The
entire dissociation process at 1200 K lasted 12 ps, or 30
metasteps, which is substantially shorter than what is required
at 700 K, for example, 41.2 ps (103 metasteps). Heating further,
to 1500 K and above, the enthalpy evolution proceeds straight
downhill with no outstanding intermediate stages. The enthalpy
release in the thermal dissociation is enormously large, that is,
0.9 eV/atom, along with a considerable volume expansion of
∼46% (Figure 5a,b). These values, however, are still likely to be
underestimated since the actual N2 product is expected to be in
the gas phase, while metadynamics simulation was performed in
the crystalline phase. Regardless, the metadynamics simulations
employed here reveal a kinetically stable range for the N6
crystal under ambient conditions, which is critical for the
practical application of this novel material.
■ SUMMARY
As potential high-energy density materials, allotropic mod-
ifications of nitrogen have been actively investigated by both
experiment and theory. Here we predict a new molecular crystal
of nitrogen consisting of novel N6 molecules, instead of
ordinary N2. The constituent N6 molecule has a charge-transfer
open-chain structure that is stabilized by strong electrostatic
interactions in the solid. Metadynamics simulations revealed
this crystal to be metastable at ambient conditions, and to
dissociate to N2 molecules at temperatures above 700 K.
Because of the large energy difference between the N−N and
NN bonds, dissociation of the N6 crystal is expected to
release a large amount of energy (∼185 kcal mol−1). At ambient
conditions, the N6 crystal is thermodynamically much more
stable than the previously synthesized cubic gauche phase of
nitrogen. The N6 crystal also has considerable kinetic stability
around room temperature, which may be sufficient for an
ambient-pressure recovery. The results obtained in this study
provide new insight into the understanding of nitrogen
allotropes, and we hope these new results will stimulate future
experimental exploration into the synthesis of this material.
DOI: 10.1021/acs.jpca.6b01655
J. Phys. Chem. A 2016, 120, 2920−2925
The Journal of Physical Chemistry A
Figure 5. Dissociation of the crystalline N6. Evolutions of the (a) volume and (b) enthalpy of the N6 crystal at ambient pressure and T = 300, 700,
1200, and 1500 K. (c) Instantaneous simulation cell at selected metasteps from the simulation at T = 1200 K. The N6 and N2 molecules are colored
blue and red, respectively.
ASSOCIATED CONTENT
■
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpca.6b01655.
Details of optimized geometries of the gas-phase N6
isomers; molecular orbitals, thermodynamic stability and
Natural bond orbital analysis of the C2h isomer; structure
parameters of the predicted crystalline N6 phase; phonon
dispersion relations for the crystalline N6 structure;
analysis of the van der Waals interactions in nitrogen
crystals. (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
*Phone: 86-21-64253964. E-mail: mzhang@ecust.edu.cn.
(M.Z.)
*Phone: 1-306-9666430. E-mail: yansun.yao@usask.ca. (Y.Y.)
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
M.J.G., A.M., and Y.Y. thank the ICT group at the Univ. of
Saskatchewan, WestGrid, and Compute Canada for providing
computing resource. This project was supported by Natural
Sciences and Engineering Research Council of Canada
(NSERC), and by National Natural Science Foundation of
China (Grant No. 11204079).
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2925 DOI: 10.1021/acs.jpca.6b01655

J. Phys. Chem. A 2016, 120, 2920−2925