High-pressure Synthesis of Cobalt Polynitrides: Unveiling Intriguing Crystal Structures and Nitridation Behavior.

In this study, we conduct extensive high-pressure experiments to investigate phase stability in the cobalt-nitrogen system. Through a combination of synthesis in a laser-heated diamond anvil cell, first-principles calculations, Raman spectroscopy, and single-crystal X-ray diffraction, we establish the stability fields of known high-pressure phases, hexagonal NiAs-type CoN, and marcasite-type CoN2 within the pressure range of 50-90 GPa. We synthesize and characterize previously unknown nitrides, Co3N2, Pnma-CoN and two polynitrides, CoN3 and CoN5, within the pressure range of 90-120 GPa. Both polynitrides exhibit novel types of polymeric nitrogen chains and networks. CoN3 feature branched-type nitrogen trimers (N3) and CoN5 show π-bonded nitrogen chain. As the nitrogen content in the cobalt nitride increases, the CoN6 polyhedral frameworks transit from face-sharing (in CoN) to edge-sharing (in CoN2 and CoN3), and finally to isolated (in CoN5). Our study provides insights into the intricate interplay between structure evolution, bonding arrangements, and high-pressure synthesis in polynitrides, expanding the knowledge for the development of advanced energy materials.

Single-Crystal Diffraction, Raman Spectroscopy, and Density Functional Theory of DTO [N-(1,7-Dinitro-1,2,6,7-tetrahydro-[1,3,5]triazino[1,2-c][1,3,5]oxadiazin-8(4H)-ylidene)nitramide].

A combined experimental and modeling study of energetic compound N-(1,7-dinitro-1,2,6,7-tetrahydro-[1,3,5]triazino[1,2-c][1,3,5]oxadiazin-8(4H)-ylidene)nitramide [C5H6N8O7, (DTO)] has been performed. We report its crystal structure, solid-phase heat of formation, and its vibrational and electronic structure obtained by single-crystal X-ray diffractometry, Raman spectroscopy, and density functional theory (DFT). DTO exhibits two adjoining six-membered rings, a triazine ring (C3N3) and an oxadiazine ring (C3N2O) ring containing two nitro functional groups and one nitroamino group. DTO crystallizes with four molecules in its unit cell and presents a density of 1.862 kg/m3 at 298 K, in excellent agreement with both DFT calculations performed both at the molecular level using the B3LYP with the 6-311+G** basis set and the solid-state level using the hybrid functional HSE6 optimized with norm-conserving pseudopotentials. The calculated vibrational structure allows for the symmetry assignment of key Raman modes in terms of atomic movements, and the calculated frequency values are in good agreement with experiment. The solid-phase DFT calculations reveal that the N atoms of the triazine ring contribute mostly to the density of states at the Fermi level. In addition, we present and discuss the computed solid-phase heat of formation (215.9 kJ/mol) and molecular electrostatic potential surface of DTO and compare them to complementary materials.

Stabilization of pentazolate anions in the high-pressure compounds Na2N5 and NaN5 and in the sodium pentazolate framework NaN5·N2.

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 the energy output and stability may be achieved if polynitrogen units are stabilized by resonance as in cyclo-N5- pentazolate salts. Here we demonstrate the synthesis of three oxygen-free pentazolate salts Na2N5, NaN5 and NaN5·N2 from sodium azide NaN3 and molecular nitrogen N2 at ∼50 GPa. NaN5·N2 is a metal-pentazolate framework (MPF) obtained via a self-templated synthesis method with nitrogen molecules being incorporated into the nanochannels of the MPF. Such self-assembled MPFs may be common in a variety of ionic pentazolate compounds. The formation of Na2N5 demonstrates that the cyclo-N5 group can accommodate more than one electron and indicates the great accessible compositional diversity of pentazolate salts.

Dinitrogen as a Universal Electron Acceptor in Solid-State Chemistry: An Example of Uncommon Metallic Compounds Na3(N2)4 and NaN2.

With the exception of lithium, alkali metals do not react with elemental nitrogen either at ambient conditions or at elevated temperatures, requiring the search for alternative synthetic routes to their nitrogen-containing compounds. Here using a controlled decomposition of sodium azide (NaN3) at high pressure conditions, we synthesize two novel compounds, Na3(N2)4 and NaN2, both containing dinitrogen anions. NaN2 synthesized at 4 GPa might be the common intermediate in high-pressure solid-state metathesis reactions, where NaN3 is used as a source of nitrogen, while Na3(N2)4 opens a new class of compounds, where [N2] units accommodate a noninteger formal charge of 0.75-. This finding can dramatically extend the expected compositions in other group 1 and 2 metal-nitrogen systems. Electronic structure calculations show the metallic character for both compounds.

Density Functional Theory and Experimental Studies of the Molecular, Vibrational, and Crystal Structure of Bis-Oxadiazole-Bis-Methylene Dinitrate (BODN).

Density function theory (DFT) and experimental characterization of energetic materials play important roles in understanding molecular structure-property relations and validating models for their predictive capabilities. Here, we report our modeling and experimental results on the molecular, vibrational, and crystal structure of energetic bis-oxadiazole-bis-methylene dinitrate (BODN) obtained by molecular DFT (M-DFT) at the B3LYP- 6-31G** level, crystal DFT (C-DFT) using the Perdew-Burke-Ernzerhof functional optimized with norm-conserving pseudopotentials, X-ray diffractometry, infrared and Raman spectroscopy, and thermogravimetric analysis. Both models predict well the experimental bond lengths, bond angles, and torsion angles of BODN. The C-DFT lattice constant values are in excellent agreement with those determined experimentally, with unit cell length and angle values differing by less than 1.2 and 0.7%, respectively. BODN presents van der Waals O···H and O···C bifurcated intramolecular contacts and short N···H and O···O intermolecular contacts. Overall, the predicted vibrational energies of both models are in line with experiment. M-DFT thermodynamic calculations predict well the experimentally derived lattice energy (-131 kJ/mol) and the M-DFT electrostatic potential calculations reveal a low sensitivity to impact. In addition, C-DFT band gap calculations predict a value of 3.80 eV for BODN, resulting predominantly from the ring O and N atoms, suggesting it is insensitive to impact. These results are compared and contrasted with those obtained in this study or reported previously for 3,3-bis-isoxazole-5,5'-bis-methylene dinitrate (BIDN).

Cyanoacetohydrazide under Pressure: Chemical Changes in a Hydrogen-Bonded Material.

Cyanoacetohydrazide (CAH, C3H5N3O) has been studied under pressure using diamond anvil cell techniques. CAH was characterized using Raman spectroscopy to 30 GPa and synchrotron X-ray diffraction to 45 GPa. The Raman spectra of CAH show reasonable qualitative agreement with first-principle calculations. The X-ray data reveal that CAH maintains its monoclinic structure to approximately 22 GPa with a density change of 12% over this range. Near 22 GPa, the Raman modes and most of the X-ray diffraction peaks disappear. These pressure-induced changes are irreversible upon the release of pressure, and the transformed sample can be recovered to ambient pressure. The recovered sample is photosensitive and shows reaction even at low laser powers of 10 mW at 532 nm. The paper concludes with observations of the roles of hydrogen bonding, molecular configurations, and the behavior of the cyano group in the pressure-induced changes in CAH.

The local atomic structures of liquid CO at 3.6†GPa and polymerized CO at 0 to 30†GPa from high-pressure pair distribution function analysis.

The local atomic structures of liquid and polymerized CO and its decomposition products were analyzed at pressures up to 30 GPa in diamond anvil cells by X-ray diffraction, pair distribution function (PDF) analysis, single-crystal diffraction, and Raman spectroscopy. The structural models were obtained by density functional calculations. Analysis of the PDF of a liquid CO-rich phase revealed that the local structure has a pronounced short-range order. The PDFs of polymerized amorphous CO at several pressures revealed the compression of the molecular structure; covalent bond lengths did not change significantly with pressure. Experimental PDFs could be reproduced with simulations from DFT-optimized structural models. Likely structural features of polymerized CO are thus 4- to 6-membered rings (lactones, cyclic ethers, and rings decorated with carbonyl groups) and long bent chains with carbonyl groups and bridging atoms. Laser heating polymerized CO at pressures of 7 to 9 GPa and 20 GPa resulted in the formation of CO(2).

Step structures on III-V phosphide (001) surfaces: how do steps and Sb affect CuPt ordering of GaInP2?

The observation of III-V phosphide (001)-(2 x 2) surfaces makes it possible to solve a long standing mystery of step structures. First-principles calculations show that a bulklike type-B step on a hydrogenated 2 x 2 surface is more stable than a rebonded one by 1.1 eV/unit step. In contrast, this energy difference for a H-free beta(2 x 4) surface is only 0.5 eV/unit step. The large difference explains why the CuPt ordering of GaInP is stronger in metal-organic chemical vapor deposition than in molecular beam epitaxy. However, a minute amount of Sb will preferentially attach to the 2 x 2 surface steps and induce additional step structures that cause ordering disruption.

Borderline magic clustering: the fabrication of tetravalent Pb cluster arrays on Si(111)-(7x7) surfaces.

Well-ordered arrays of identical Pb clusters have been fabricated on a Si(111)-(7x7) substrate by the temperature-mediated surface clustering method. Interestingly, these clusters can easily transform into other forms when the growth temperature deviates slightly from the optimal values. In accord with experiments, first-principle total-energy calculations reveal several cluster structures centered on a mixed cluster model involving surface Pb and Si exchange. This borderline Pb/Si(111) system provides a unique, controlled way to study surface magic cluster formation and breakup dynamics.

Growth model for atomic ordering: the case for quadruple-period ordering in GaAsSb alloys.

Quadruple-period ordering in GaAsSb alloys is studied both theoretically and experimentally. A growth model is proposed to account for the observed three-dimensional (3D) ordered structure. The model is qualitatively different from the widely accepted surface reconstruction and dimerization-induced ordering models that strictly speaking explain only the in-plane 2D patterns. Here, we show that the already ordered substrate will affect the reconstruction of the growth front with respect to the substrate to ensure a correct stacking of the individual 2D ordered layers into the observed 3D lattice.

Strain-driven mesoscopic reconstruction of the As/Ge(111) surface.

Periodic arrays of large hexagonal tiles (up to 170 A in size) are observed on As/Ge(111) surfaces. First-principles total energy calculations combined with scanning tunneling microscopy reveal a (5-7-5)-ringed structure for the trenches that separate the tiles. We find that trenches form via an exothermic process. The calculated equilibrium trench spacing of approximately 104 A agrees with experiment. Comparison between first-principles calculations and continuum elasticity theory suggests that the observed mesoscopic reconstruction is driven entirely by long-range surface strain relaxation.