Single-Step Mechanism for Regioselective Nitration of 9,10-BN-Napthalene with Acetyl Nitrate in the Gas Phase.

The energetics of the regioselective mononitration of 9,10-BN-naphthalene with acetyl nitrate (H3C2NO4) were modeled with ab initio simulations in the gas phase and an acetonitrile solvent. The single-electron-transfer (SET) nitration mechanism leading to a σ-complex and a single-step nitration mechanism were modeled. The energy barrier for the single-step mechanism was lower than that for the SET mechanism in the gas phase. However, the two are much more energetically competitive in the solvent. The σ-complex was found to be unstable in the gas phase owing to the interaction with the counterion. Using the single-step mechanism, the carbon site 1 nearest boron had the lowest activation energy for nitration of 22.6 kcal/mol, while site 3 had the second lowest barrier of 24.6 kcal/mol. Details on the molecular structures at intermediate and transition states as well as charges in different configurations are discussed.

Predicted Reaction Mechanisms, Product Speciation, Kinetics, and Detonation Properties of the Insensitive Explosive 2,6-Diamino-3,5-dinitropyrazine-1-oxide (LLM-105).

2,6-Diamino-3,5-dinitropyrazine-1-oxide (LLM-105) is a relatively new and promising insensitive high-explosive (IHE) material that remains only partially characterized. IHEs are of interest for a range of applications and from a fundamental science standpoint, as the root causes behind insensitivity are poorly understood. We adopt a multitheory approach based on reactive molecular dynamic simulations performed with density functional theory, density functional tight-binding, and reactive force fields to characterize the reaction pathways, product speciation, reaction kinetics, and detonation performance of LLM-105. We compare and contrast these predictions to 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), a prototypical IHE, and 1,3,5,7-tetranitro-1,3,5,7-tetrazoctane (HMX), a more sensitive and higher performance material. The combination of different predictive models allows access to processes operative on progressively longer timescales while providing benchmarks for assessing uncertainties in the predictions. We find that the early reaction pathways of LLM-105 decomposition are extremely similar to TATB; they involve intra- and intermolecular hydrogen transfer. Additionally, the detonation performance of LLM-105 falls between that of TATB and HMX. We find agreement between predictive models for first-step reaction pathways but significant differences in final product formations. Predictions of detonation performance result in a wide range of values, and one-step kinetic parameters show the similar reaction rates at high temperatures for three out of four models considered.

High-Pressure Equation of State of 1,3,5-triamino-2,4,6-trinitrobenzene: Insights into the Monoclinic Phase Transition, Hydrogen Bonding, and Anharmonicity.

The high-pressure equation of state (EOS) of energetic materials (EMs) is important for continuum and mesoscale models of detonation performance and initiation safety. Obtaining a high-fidelity EOS of the insensitive EM 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) has proven to be difficult because of challenges in experimental characterization at high pressures (HPs). In this work, powder X-ray diffraction patterns were fitted using the recently discovered monoclinic I2/a phase above 4 GPa, which shows that TATB is less compressible than when indexed with the triclinic P1̅ phase. First-principles calculations were performed with Perdew-Burke-Ernzerhof (PBE) and PBE0 functionals including thermal effects using the P1̅ phase. PBE0 improves the description of hydrogen bonding and thus predicts accurate planar a and b lattice parameters under ambient conditions. However, discrepancies in the predicted lattice parameters above 4-10 GPa compared with experimental measurements indexed with P1̅ are further evidence of a structural modification at high pressure. Layer sliding defects are formed during molecular dynamics simulations, which induces an anharmonic effect on the thermal expansion of the c lattice parameter. In short, the results provide several insights into determining high-fidelity EOS parameters for TATB and other molecular crystals.

Novel phases and superconductivity of tin sulfide compounds.

Tin sulfides, Sn x S y , are an important class of materials that are actively investigated as novel photovoltaic and water splitting materials. A first-principles evolutionary crystal structure search is performed with the goal of constructing the complete phase diagram of Sn x S y and discovering new phases as well as new compounds of varying stoichiometry at ambient conditions and pressures up to 100 GPa. The ambient phase of SnS2 with P 3 ¯ m 1 symmetry remains stable up to 28 GPa. Another ambient phase, SnS, experiences a series of phase transformations including α-SnS to ß-SnS at 9 GPa, followed by ß-SnS to γ-SnS at 40 GPa. γ-SnS is a new high-pressure metallic phase with P m 3 ¯ m space group symmetry stable up to 100 GPa, which becomes a superconductor with a maximum T c = 9.74 K at 40 GPa. Another new metallic compound, Sn3S4 with I 4 ¯ 3 d space group symmetry, is predicted to be stable at pressures above 15 GPa, which also becomes a superconductor with relatively high T c = 21.9 K at 30 GPa.

Ternary Inorganic Compounds Containing Carbon, Nitrogen, and Oxygen at High Pressures.

Ternary CxNyOz 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 CxNyOz compounds. In this work, first-principles variable-composition evolutionary structure prediction calculations are performed with the goal of discovering novel mixed CxNyOz 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 C2N2O crystal containing an extended covalent network of C, N, and O atoms, having space group symmetry Cmc21, and stable above just 10 GPa. Several other novel metastable (CO)x-(N)y crystalline compounds discovered during the search, including two polymorphs of C2NO2 and two polymorphs of C3N2O3 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 (N5H) and ammonium pentazolate (NH4)(N5), both featuring cyclo-N5- are discovered using a first-principles evolutionary search of the nitrogen-rich portion of the hydro-nitrogen binary phase diagram (NxHy, x ≥ y) at high pressures. Both crystals consist of the pentazolate N5- anion and ammonium NH4+ or hydrogen H+ cations. These two crystals are predicted to be thermodynamically stable at pressures above 30 GPa for (NH4)(N5) and 50 GPa for pentazole N5H. The chemical transformation of ammonium azide (NH4)(N3) mixed with dinitrogen (N2) to ammonium pentazolate (NH4)(N5) 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 (RxNy; R = Li, Na, and Cs) have been predicted to be stable at high pressures and one of them, CsN5 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 N4 chains, N5 rings, and N6 rings stable at high pressures are discovered. In addition, an unusual nitrogen-rich metallic crystal with stoichiometry K2N16 consisting of a planar two-dimensional extended network of nitrogen atoms arranged in fused 18 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 K2N16 compound are investigated, and the pressure-dependent IR spectrum is obtained to assist in experimental discovery of this new high-nitrogen content material.

Novel rubidium poly-nitrogen materials at high pressure.

First-principles crystal structure search is performed to predict novel rubidium poly-nitrogen materials at high pressure by varying the stoichiometry, i.e., relative quantities of the constituent rubidium and nitrogen atoms. Three compounds of high nitrogen content, RbN5, RbN2, and Rb4N6, are discovered. Rubidium pentazolate (RbN5) becomes thermodynamically stable at pressures above 30 GPa. The charge transfer from Rb to N atoms enables aromaticity in cyclo-N5- while increasing the ionic bonding in the crystal. Rubidium pentazolate can be synthesized by compressing rubidium azide (RbN3) and nitrogen (N2) precursors above 9.42 GPa, and its experimental discovery is aided by calculating the Raman spectrum and identifying the features attributed to N5- modes. The two other interesting compounds, RbN2 containing infinitely long single-bonded nitrogen chains and Rb4N6 consisting of single-bonded N6 hexazine rings, become thermodynamically stable at pressures exceeding 60 GPa. In addition to the compounds with high nitrogen content, Rb3N3, a new compound with 1:1 RbN stoichiometry containing bent N3 azides is found to exist at high pressures.

New phase of ammonium nitrate: A monoclinic distortion of AN-IV.

A new phase of ammonium nitrate (AN) is found using first principles evolutionary crystal structure search. It is this polymorph that is associated with the phase transition to previously unidentified phase, which was detected in experiment at 17 GPa upon appearance of the two extra peaks in Raman spectrum. The new phase has a monoclinic unit cell in the P21/m space group symmetry (AN-P21/m) and is similar to the known phase IV of AN (AN-IV) except the ammonium molecules are oriented differently relative to the nitrate molecules. The calculated free energy of AN-P21/m is found to be lower than AN-IV at pressures above 10.83 GPa. The equation of state of both AN-P21/m and AN-IV phases (volume vs hydrostatic pressure at room temperature) has been obtained within the quasi-harmonic approximation. The calculated Raman spectrum of both AN-P21/m and AN-IV as a function of pressure is in a good agreement with experiment. The energetic competitiveness of AN-IV and AN-P21/m at ambient conditions suggests a possibility of the phase transition in a small pressure-temperature range near ambient pressure and temperature.

Ab initio structural dynamics of pure and nitrogen-containing amorphous carbon.

Amorphous carbon (a-C) has attracted considerable interest due to its desirable properties, which are strongly dependent on its structure, density and impurities. Using ab initio molecular dynamics simulations we show that the sp2/sp3 content and underlying structural order of a-C produced via liquid quenching evolve at high temperatures and pressures on sub-nanosecond timescales. Graphite-like densities ([Formula: see text] 2.7 g/cc) favor the formation of layered arrangements characterized by sp2 disordered bonding resembling recently synthesized monolayer amorphous carbon (MAC), while at diamond-like densities ([Formula: see text] 3.3 g/cc) the resulting structures are dominated by disordered tetrahedral sp3 hybridization typical of diamond-like amorphous carbon (DLC). At intermediate densities the system is a highly compressible mixture of coexisting sp2 and sp3 regions that continue to segregate over 10's of picoseconds. The addition of nitrogen (20.3%) (a-CN) generates major system features similar with those of a-C, but has the unexpected effect of reinforcing the thermodynamically disfavored carbon structural motifs at low and high densities, while inhibiting phase separation in the intermediate region. At the same time, no nitrogen elimination from the carbon framework is observed above [Formula: see text] 2.8 g/cc, suggesting that nitrogen impurities are likely to remain embedded in the carbon structures during fast temperature quenches at high pressures.

Ab Initio Crystal Structure Prediction of the Energetic Materials LLM-105, RDX, and HMX.

Crystal structure prediction (CSP) is performed for the energetic materials (EMs) LLM-105 and α-RDX, as well as the α and ß conformational polymorphs of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), using the genetic algorithm (GA) code, GAtor, and its associated random structure generator, Genarris. Genarris and GAtor successfully generate the experimental structures of all targets. GAtor's symmetric crossover scheme, where the space group symmetries of parent structures are treated as genes inherited by offspring, is found to be particularly effective. However, conducting several GA runs with different settings is still important for achieving diverse samplings of the potential energy surface. For LLM-105 and α-RDX, the experimental structure is ranked as the most stable, with all of the dispersion-inclusive density functional theory (DFT) methods used here. For HMX, the α form was persistently ranked as more stable than the ß form, in contrast to experimental observations, even when correcting for vibrational contributions and thermal expansion. This may be attributed to insufficient accuracy of dispersion-inclusive DFT methods or to kinetic effects not considered here. In general, the ranking of some putative structures is found to be sensitive to the choice of the DFT functional and the dispersion method. For LLM-105, GAtor generates a putative structure with a layered packing motif, which is desirable thanks to its correlation with low sensitivity. Our results demonstrate that CSP is a useful tool for studying the ubiquitous polymorphism of EMs and shows promise of becoming an integral part of the EM development pipeline.

Mechanochemical synthesis of glycine oligomers in a virtual rotational diamond anvil cell.

Mechanochemistry of glycine under compression and shear at room temperature is predicted using quantum-based molecular dynamics (QMD) and a simulation design based on rotational diamond anvil cell (RDAC) experiments. Ensembles of high throughput semiempirical density functional tight binding (DFTB) simulations are used to identify chemical trends and bounds for glycine chemistry during rapid shear under compressive loads of up to 15.6 GPa. Significant chemistry is found to occur during compressive shear above 10 GPa. Recovered products consist of small molecules such as water, structural analogs to glycine, heterocyclic molecules, large oligomers, and polypeptides including the simplest polypeptide glycylglycine at up to 4% mass fraction. The population and size of oligomers generally increases with pressure. A number of oligomeric polypeptide precursors and intermediates are also identified that consist of two or three glycine monomers linked together through C-C, C-N, and/or C-O bridges. Even larger oligomers also form that contain peptide C-N bonds and exhibit branched structures. Many of the product molecules exhibit one or more chiral centers. Our simulations demonstrate that athermal mechanical compressive shearing of glycine is a plausible prebiotic route to forming polypeptides.

An Isosymmetric High-Pressure Phase Transition in α-Glycylglycine: A Combined Experimental and Theoretical Study.

We investigated the effects of hydrostatic pressure on α-glycylglycine (α-digly) using a combined experimental and theoretical approach. The results of powder X-ray diffraction show a change in compressibility of the axes above 6.7 GPa, but also indicate that the structure remains in the same monoclinic space group, suggesting an isosymmetric phase transition. A noticeable change in the Raman spectra between 6 and 7.5 GPa further supports the observed phase transition. First-principles-based calculations combined with the crystal structure prediction code USPEX predict a number of possible polymorphs at high pressure. An orthorhombic structure with a bent peptide backbone is the lowest enthalpy polymorph above 6.4 GPa; however, it is not consistent with experimental observations. A second monoclinic structure isosymmetric to α-digly, α'-digly, is predicted to become more stable above 11.4 GPa. The partial atomic charges in α'-digly differ from α-digly, and the molecule is bent, possibly indicating different reactivity of α'-digly. The similarity in the lattice parameters predicted from calculations and the axial changes observed experimentally support that the α'-digly phase is likely observed at high pressure. A possible explanation for the isosymmetric phase transition is discussed in terms of relaxing strained hydrogen bonding interactions. Such combined experimental and modeling efforts provide atomic-level insight into how pressure-driven conformational changes alter hydrogen-bonding networks in complicated molecular crystals.