Ternary inorganic compounds containing carbon, nitrogen, and oxygen at high pressures

Ternary C_{x}N_{y}O_{z} compounds are actively researched as novel high energy density and ultrahard materials. Although some synthesis work has been performed at ambient conditions, very little is known about the high pressure chemistry of of C_{x}N_{y}O_{z} compounds. In this work, first principles variable-composition evolutionary structure prediction calculations are performed with the goal of discovering novel mixed C_{x}N_{y}O_{z} materials at ambient and high pressure conditions. By systematically searching ternary variable composition crystalline materials, the full ternary phase diagram is constructed in the range of pressures from 0 to 100 GPa. The search finds the C_{2}N_{2}O crystal containing extended covalent network of C, N, and O atoms, having space group symmetry Cmc2_{1}, and stable above just 10 GPa. Several other novel metastable (CO)_{x}-(N)_{y} crystalline compounds discovered during the search, including two polymorphs of C_{2}NO_{2} and two polymorphs of C_{3}N_{2}O_{3} crystals are found to be energetically favorable compared to polymeric carbon monoxide (CO) and nitrogen. Predicted new compounds are characterized by their Raman spectra and equations of state

Pentazole and Ammonium Pentazolate: Crystalline Hydro-Nitrogens at High Pressure

Two new crystalline compounds, pentazole (N_{5}H) and ammonium pentazolate (NH_{4})(N_{5}), both featuring cyclo-{\rm N_{5}^{-}} are discovered using first principles evolutionary search of the nitrogen-rich portion of the hydro-nitrogen binary phase diagram (N_{x}H_{y}, x\geqy) at high pressures. Both crystals consist of the pentazolate N_{5}^{-} anion and ammonium NH_{4}^{+} or hydrogen H^{+} cations. These two crystals are predicted to be thermodynamically stable at pressures above 30 GPa for (NH_{4})(N_{5}) and 50 GPa for pentazole N_{5}H. The chemical transformation of ammonium azide (NH_{4})(N_{3}) mixed with di-nitrogen (N_{2}) to ammonium pentazolate (NH_{4})(N_{5}) is predicted to become energetically favorable above 12.5 GPa. To assist in identification of newly synthesized compounds in future experiments, the Raman spectra of both crystals are calculated and mode assignments are made as a function of pressure up to 75 GPa

Novel Potassium Polynitrides at High Pressures

Polynitrogen compounds have attracted great interest due to their potential applications as high energy density materials. Most recently, a rich variety of alkali polynitrogens (R_{x}N_{y}; R=Li, Na, and Cs) have been predicted to be stable at high pressures and one of them, CsN_{5} has been recently synthesized. In this work, various potassium polynitrides are investigated using first-principles crystal structure search methods. Several novel molecular crystals consisting of N_{4} chains, N_{5} rings, and N_{6} rings stable at high pressures are discovered. In addition, an unusual nitrogen-rich metallic crystal with stoichiometry K_{2}N_{16} consisting of a planar two-dimensional extended network of nitrogen atoms arranged in fused eighteen atom rings is found to be stable above 70 GPa. An appreciable electron transfer from K to N atoms is responsible for the appearance of unexpected chemical bonding in these crystals. The thermodynamic stability and high pressure phase diagram is constructed. The electronic and vibrational properties of the layered polynitrogen K_{2}N_{16} compound are investigated, and the pressure-dependent IR-spectrum is obtained to assist in experimental discovery of this new high-nitrogen content material

Anisotropic constitutive relationships in energetic materials: PETN and HMX

This paper presents results of first-principles density functional calculations of the equation of state (EOS) of PETN-I and beta-HMX. The isotropic EOS for hydrostatic compression has been extended to include uniaxial compressions in the [100], [010], [001], [110], [101], [011], and [111] directions up to compression ratio V/V0 = 0.70. Equilibrium properties, including lattice parameters and elastic constants, as well as hydrostatic EOS are in good agreement with available experimental data. The shear stresses of uniaxially compressed PETN-I and beta-HMX have been evaluated and their behavior as a function of compression ratio has been used to make predictions of shock sensitivity of these EMs. A comparison of predicted sensitivities with available experimental data has also been performed

First-principles anisotropic constitutive relationships in β-cyclotetramethylene tetranitramine (β-HMX)

First-principles density functional theory calculations have been performed to obtain constitutive relationships in the crystalline energetic material β-cyclotetramethylene tetranitramine (β-HMX). In addition to hydrostatic loading, uniaxial compressions in the directions normal to the {100}, {010}, {001}, {110}, {101}, {011}, and {111} planes have been performed to investigate the anisotropic equation of state (EOS). The calculated lattice parameters and hydrostatic EOS are in reasonable agreement with the available experimental data. The uniaxial compression data show a significant anisotropy in the principal stresses, change in energy, band gap, and shear stresses, which might lead to the anisotropy of the elastic-plastic shock transition and shock sensitivity of β-HMX

Nanoscale Molecular Dynamics Simulaton of Shock Compression of Silicon

We report results of molecular dynamics simulation of shock wave propagation in silicon in [100], [110], and [111] directions obtained using a classical environment-dependent interatomic potential (EDIP). Several regimes of materials response are classified as a function of shock wave intensity using the calculated shock Hugoniot. Shock wave structure in [100] and [111] directions exhibit usual evolution as a function of piston velocity. At piston velocities km/s the shock wave consists of a fast elastic precursor followed by a slower plastic front. At larger piston velocities the single overdriven plastic wave propagates through the crystal causing amorphitization of Si. However, the [110] shock wave exhibits an anomalous materials response at intermediate piston velocities around km/s which is characterized by the absence of plastic deformations

Density functional theory calculations of anisotropic constitutive relationships in alpha-cyclotrimethylenetrinitramine

Constitutive relationships in the crystalline energetic material alpha-cyclotrimethylenetrinitramine (alpha-RDX) have been investigated using first-principles density functional theory. The equilibrium properties of alpha-RDX including unit cell parameters and bulk modulus, as well as the hydrostatic equation of state (EOS), have been obtained and compared with available experimental data. The isotropic EOS has been extended to include the anisotropic response of alpha-RDX by performing uniaxial compressions normal to several low-index planes, {100}, {010}, {001}, {110}, {101}, {011}, and {111}, in the Pbca space group. The uniaxial-compression data exhibit a considerable anisotropy in the principal stresses, changes in energy, band gaps, and shear stresses, which might play a role in the anisotropic behavior of alpha-RDX under shock loading

First-principles investigation of anisotropic constitutive relationships in pentaerythritol tetranitrate

First-principles density functional theory (DFT) calculations have been used to obtain the constitutive relationships of pentaerythritol tetranitrate (PETN-I), a crystalline energetic material. The isotropic equation of state (EOS) for hydrostatic compression has been extended to include uniaxial compressions in the , , , , , , and crystallographic directions up to a compression ratio of V/V0=0.70. DFT predicts equilibrium properties such as lattice parameters and elastic constants, as well as the hydrostatic EOS, in agreement with available experimental data. Our results show a substantial anisotropy of various properties of PETN-I upon uniaxial compression. To characterize the anisotropic traits of PETN, different physical properties of the uniaxially compressed crystal such as the energy per atom, band gap, and stress tensor have been evaluated as a function of compression ratio. The maximum shear stresses were calculated and examined for a correlation with the anisotropy in shock-initiation sensitivity