Extreme Metastability of Diamond and its Transformation to the BC8 Post-Diamond Phase of Carbon.

Diamond possesses exceptional physical properties due to its remarkably strong carbon-carbon bonding, leading to significant resilience to structural transformations at very high pressures and temperatures. Despite several experimental attempts, synthesis and recovery of the theoretically predicted post-diamond BC8 phase remains elusive. Through quantum-accurate multimillion atom molecular dynamics (MD) simulations, we have uncovered the extreme metastability of diamond at very high pressures, significantly exceeding its range of thermodynamic stability. We predict the post-diamond BC8 phase to be experimentally accessible only within a narrow high pressure-temperature region of the carbon phase diagram. The diamond to BC8 transformation proceeds through premelting followed by BC8 nucleation and growth in the metastable carbon liquid. We propose a double-shock compression pathway for BC8 synthesis, which is currently being explored in experiments at the National Ignition Facility.

N,N-Bis(2,4-Dibenzhydryl-6-cycloalkylphenyl)butane-2,3-diimine-Nickel Complexes as Tunable and Effective Catalysts for High-Molecular-Weight PE Elastomers.

Four examples of N,N-bis(aryl)butane-2,3-diimine-nickel(II) bromide complexes, [ArN=C(Me)-C(Me)=NAr]NiBr2 (where Ar = 2-(C5H9)-4,6-(CHPh2)2C6H2 (Ni1), Ar = 2-(C6H11)-4,6-(CHPh2)2C6H2 (Ni2), 2-(C8H15)-4,6-(CHPh2)2C6H2 (Ni3) and 2-(C12H23)-4,6-(CHPh2)2C6H2 (Ni4)), disparate in the ring size of the ortho-cycloalkyl substituents, were prepared using a straightforward one-pot synthetic method. The molecular structures of Ni2 and Ni4 highlight the variation in the steric hindrance of the ortho-cyclohexyl and -cyclododecyl rings exerted on the nickel center, respectively. By employing EtAlCl2, Et2AlCl or MAO as activators, Ni1-Ni4 displayed moderate to high activity as catalysts for ethylene polymerization, with levels falling in the order Ni2 (cyclohexyl) > Ni1 (cyclopentyl) > Ni4 (cyclododecyl) > Ni3 (cyclooctyl). Notably, cyclohexyl-containing Ni2/MAO reached a peak level of 13.2 × 106 g(PE) of (mol of Ni)-1 h-1 at 40 °C, yielding high-molecular-weight (ca. 1 million g mol-1) and highly branched polyethylene elastomers with generally narrow dispersity. The analysis of polyethylenes with 13C NMR spectroscopy revealed branching density between 73 and 104 per 1000 carbon atoms, with the run temperature and the nature of the aluminum activator being influential; selectivity for short-chain methyl branches (81.8% (EtAlCl2); 81.1% (Et2AlCl); 82.9% (MAO)) was a notable feature. The mechanical properties of these polyethylene samples measured at either 30 °C or 60 °C were also evaluated and confirmed that crystallinity (Xc) and molecular weight (Mw) were the main factors affecting tensile strength and strain at break (εb = 353-861%). In addition, the stress-strain recovery tests indicated that these polyethylenes possessed good elastic recovery (47.4-71.2%), properties that align with thermoplastic elastomers (TPEs).

Crystal structure of silver pentazolates AgN5 and AgN6.

Silver pentazolate, a high energy density compound containing the cyclo-N5- anion, has recently been synthesized under ambient conditions. However, due to high sensitivity to irradiation, its crystal structure has not been determined. In this work, silver-nitrogen crystalline compounds under ambient conditions and at high pressures, up to 100 GPa, are predicted and characterized by performing first-principles evolutionary crystal structure searching with variable stoichiometry. It is found that newly discovered AgN5 and AgN6 are the only thermodynamically stable silver-nitrogen compounds at pressures between 42 and 80 GPa. In contrast to AgN5, the pentazolate AgN6 compound contains N2 diatomic molecules in addition to cyclo-N5-. These AgN5 and AgN6 crystals are metastable under ambient conditions with positive formation enthalpies of 54.95 kJ mol-1 and 46.24 kJ mol-1, respectively. The underlying cause of the stability of cyclo-N5- silver pentazolates is the enhanced aromaticity enabled by the charge transfer from silver atoms to nitrogen rings. To aid in the experimental identification of these materials, calculated Raman spectra are reported at ambient pressure: the frequencies of N5- vibrational modes of AgN5 are in good agreement with those measured in the experiment.

High molecular weight polyethylenes of narrow dispersity promoted using bis(arylimino)cyclohepta[b]pyridine-cobalt catalysts ortho-substituted with benzhydryl & cycloalkyl groups.

A one-pot template strategy has been utilized to synthesize sterically enhanced bis(imino)cyclohepta[b]pyridine-cobalt(ii) chlorides, [2-{(Ar)N[double bond, length as m-dash]CMe}-9-{N(Ar)}C10H10N]CoCl2 (Ar = 2-(C5H9)-4,6-(CHPh2)2C6H2Co1, 2-(C6H11)-4,6-(CHPh2)2C6H2Co2, 2-(C8H15)-4,6-(CHPh2)2C6H2Co3, 2-(C12H23)-4,6-(CHPh2)2C6H2Co4, 2,6-(C5H9)2-4-(CHPh2)C6H2Co5). All five complexes have been characterized by a combination of FT-IR spectroscopy, elemental analysis and single crystal X-ray diffraction. The molecular structures of Co1, Co3 and Co5 highlight the substantial steric hindrance imparted by the 2-cycloalkyl-6-benzhydryl or 2,6-dicyclopentyl ortho-substitution pattern; distorted square pyramidal geometries are exhibited in each case. On activation with methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all the complexes (apart from Co4/MAO) were active ethylene polymerization catalysts (up to 3.70 × 106 g PE per mol (Co) per h for Co5/MMAO), operating effectively at temperatures between 50 °C and 60 °C, producing polyethylenes with high molecular weights (up to 589.5 kg mol-1 for Co3/MAO). Furthermore, all polymers were highly linear (Tm > 130 °C) with narrow dispersities (Mw/Mn range: 2.0-3.0). The coexistence of two chain termination pathways, ß-H elimination and transfer to aluminum, has been demonstrated using 13C/1H NMR spectroscopy.

Probing the effect of ortho-cycloalkyl ring size on activity and thermostability in cycloheptyl-fused N,N,N-iron ethylene polymerization catalysts.

The syntheses of six bis(imino)-5,6,7,8-tetrahydrocycloheptapyridine-iron(ii) chloride complexes, [2-{(Ar)NCMe}-9-{N(Ar)}C10H10N]FeCl2 (Ar = 2-(C5H9)-6-MeC6H3Fe1, 2-(C6H11)-6-MeC6H3Fe2, 2-(C8H15)-6-MeC6H3Fe3, 2-(C5H9)-4,6-Me2C6H2Fe4, 2-(C6H11)-4,6-Me2C6H2Fe5, 2-(C8H15)-4,6-Me2C6H3Fe6), are reported in which the ring size of the ortho-cycloalkyl group has been varied as has the type of para-substituent. The molecular structures of Fe3 and Fe6 reveal square pyramidal geometries at iron while the ortho-cyclooctyl rings adopt boat-chair conformations. On treatment with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all six complexes showed optimal activities at 80 °C [up to 1.9 × 107 g of PE per mol Fe per h for Fe5/MMAO] for ethylene polymerization forming linear polyethylene (Tm's > 126 °C). Notably, the catalytic activities showed a marked correlation with the ring size of the ortho-cycloalkyl substituent: cyclohexyl (Fe2 and Fe5) > cyclooctyl (Fe3 and Fe6) > cyclopentyl (Fe1 and Fe4) for either para-substituent, H or Me. Furthermore, this family of iron catalysts exhibited remarkable thermostability by remaining highly active even at temperatures as high as 100 °C (1.1 × 107 g of PE per mol Fe per h); the wide variation in polymer molecular weights (Mw: 2.4-166 kg mol-1), influenced through choice of precatalyst and co-catalyst as well as by temperature and pressure, further highlights the versatility of these catalysts.

Monolayer Modification of VTe2 and Its Charge Density Wave.

Interlayer interactions in layered transition metal dichalcogenides are known to be important for describing their electronic properties. Here, we demonstrate that the absence of interlayer coupling in monolayer VTe2 also causes their structural modification from a distorted 1T' structure in bulk and multilayer samples to a hexagonal 1T structure in the monolayer. X-ray photoemission spectroscopy indicates that this structural transition is associated with electron transfer from the vanadium d bands to the tellurium atoms for the monolayer. This charge transfer may reduce the in-plane d orbital hybridization and thus favor the undistorted 1T structure. Phonon-dispersion calculations show that, in contrast to the 1T' structure, the 1T structure exhibits imaginary phonon modes that lead to a charge density wave (CDW) instability, which is also observed by low-temperature scanning tunneling microscopy as a 4 × 4 periodic lattice distortion. Thus, this work demonstrates a novel CDW material, whose properties are tuned by interlayer interactions.

Highly Linear Polyethylenes Achieved Using Thermo-Stable and Efficient Cobalt Precatalysts Bearing Carbocyclic-Fused NNN-Pincer Ligand.

Six examples of 2-(1-arylimino)ethyl-9-arylimino-5,6,7,8-tetrahydrocycloheptapyridine-cobalt(II) chloride complexes, [2-(1-ArN)C2H3-9-ArN-5,6,7,8-C5H8C5H3N]CoCl2, (Ar = 2-(C5H9)-6-MeC6H3 Co1, 2-(C6H11)-6-MeC6H3 Co2, 2-(C8H15)-6-MeC6H3 Co3, 2-(C5H9)-4,6-Me2C6H2 Co4, 2-(C6H11)-4,6-Me2C6H2 Co5, and 2-(C8H15)-4,6-Me2C6H2 Co6), were synthesized by the direct reaction of the corresponding ortho-cycloalkyl substituted carbocyclic-fused bis(arylimino)pyridines (L1⁻L6) and cobalt(II) chloride in ethanol with good yields. All the synthesized ligands (L1⁻L6) and their corresponding cobalt complexes (Co1⁻Co6) were fully characterized by FT-IR, ¹H/13C-NMR spectroscopy and elemental analysis. The crystal structure of Co2 and Co3 revealed that the ring puckering of both the ortho-cyclohexyl/cyclooctyl substituents and the one pyridine-fused seven-membered ring; a square-based pyramidal geometry is conferred around the metal center. On treatment with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), all the six complexes showed high activities (up to 4.09 × 106 g of PE mol-1 (Co) h-1) toward ethylene polymerization at temperatures between 20 °C and 70 °C with the catalytic activities correlating with the type of ortho-cycloalkyl substituent: Cyclopentyl (Co1 and Co4) > cyclohexyl (Co2 and Co5) > cyclooctyl (Co3 and Co6) for either R = H or Me and afforded strictly linear polyethylene (Tm > 130 °C). The narrow unimodal distributions of the resulting polymers are consistent with single-site active species for the precatalyst. Furthermore, compared to the previously reported cobalt analogues, the titled precatalysts exhibited good thermo-stability (up to 70 °C) and possessed longer lifetime along with a higher molecular weight of PE (Mw: 9.2~25.3 kg mol-1).

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.

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.

ortho-Cycloalkyl substituted N,N'-diaryliminoacenaphthene-Ni(ii) catalysts for polyethylene elastomers; exploring ring size and temperature effects.

A family of six unsymmetrical N,N'-diiminoacenaphthene-nickel(ii) bromide complexes, [1-{2,6-(Ph2CH)2-4-MeC6H2N}-2-(ArN)C2C10H6]NiBr2 (Ar = 2-(C6H11)-6-MeC6H2Ni1, 2-(C5H9)-6-MeC6H2Ni2, 2-(C8H15)-6-MeC6H2Ni3, 2-(C6H11)-4,6-Me2C6H2Ni4, 2-(C5H9)-4,6-Me2C6H2Ni5, 2-(C8H15)-4,6-Me2C6H2Ni6), each bearing one ring-size variable 4-R-2-methyl-6-cycloalkyl-substituted N-aryl group and one N'-4-methyl-2,6-dibenzhydrylphenyl group, have been prepared and fully characterized. The molecular structures of Ni1, Ni2, Ni3 and Ni5 reveal distorted tetrahedral geometries with different degrees of steric protection imparted by the two inequivalent N-aryl groups. On activation with either EASC or MMAO, all the precatalysts are highly active (up to 17.45 × 106 g PE mol-1 (Ni) h-1) for ethylene polymerization at 20-50 °C with their activities correlating with the type of cycloalkyl ortho-substituent: cyclooctyl (Ni6, Ni3) > the cyclopentyl (Ni5, Ni2) > cyclohexyl (Ni4, Ni1) for either R = H or Me. Moderately branched to hyperbranched polyethylenes (Tm's as low as 44.2 °C) can be obtained with molecular weights in the range 2.14-6.68 × 105 g mol-1 with the branching content enhanced by the temperature of the polymerization. Dynamic mechanical analysis (DMA) and monotonic tensile stress-strain tests have been employed on the polyethylene samples and reveal the more branched materials to show good elastic recovery properties (up to 75.5%).

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.

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.

Force distribution in a granular medium under dynamic loading.

Force distribution in a granular medium subjected to an impulse loading is investigated in experiment and computer simulations. An experimental technique is developed to measure forces acting on individual grains at the bottom of the granular sample consisting of steel balls. Discrete element method simulation also is performed under conditions mimicking those in experiment. Both theory and experiment display exponentially decaying maximum force distributions at the bottom of the sample in the range of large forces. In addition, the simulations also reveal exponential force distribution throughout the sample and uncover correlation properties of the interparticle forces during dynamic loading of the granular samples. Simulated time dependence of coordination number, orientational order parameter, correlation radius, and force distribution clearly demonstrates the nonequilibrium character of the deformation process in a granular medium under impulse loading.

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.

Laminar, cellular, transverse, and multiheaded pulsating detonations in condensed phase energetic materials from molecular dynamics simulations.

The development of condensed-phase detonation instabilities is simulated using moving window molecular dynamics and a generic AB model of a high explosive. It is found that an initially planar detonation front with one-dimensional flow can become unstable through development of transverse perturbations resulting in highly inhomogeneous and complex two- and three-dimensional distributions of pressure and other variables within the detonation front. Chemical reactions are initiated in localized transverse shock fronts and Mach stems with a pressure and temperature higher than those predicted by classic Zel'dovich, von Neumann, and Doering detonation theory. The two-dimensional cellular and transverse and three-dimensional pulsating detonation structures are found by varying the physico-chemical properties of AB energetic material, sample geometry, and boundary conditions. The different regimes of condensed-phase detonation that can develop from instabilities within a planar detonation front exhibit structures, although at a much smaller scale, that are similar to those observed in gases and diluted liquids.

Ammonium azide under high pressure: a combined theoretical and experimental study.

Efforts to synthesize, characterize, and recover novel polynitrogen energetic materials have driven attempts to subject high nitrogen content precursor materials (in particular, metal and nonmetal azides) to elevated pressures. Here we present a combined theoretical and experimental study of the high-pressure behavior of ammonium azide (NH4N3). Using density functional theory, we have considered the relative thermodynamic stability of the material with respect to two other crystal phases, namely, trans-tetrazene (TTZ), and also a novel hydronitrogen solid (HNS) of the form (NH)4, that was recently predicted to become relatively stable under high pressure. Experimentally, we have measured the Raman spectra of NH4N3 up to 71 GPa at room temperature. Our calculations demonstrate that the HNS becomes stable only at pressures much higher (89.4 GPa) than previously predicted (36 GPa). Our Raman spectra are consistent with previous reports up to lower pressures and at higher pressures, while some additional subtle behavior is observed (e.g., mode splitting), there is again no evidence of a phase transition to either TTZ or the HNS.

Evolution of shock-induced orientation-dependent metastable states in crystalline aluminum.

The evolution of orientation-dependent metastable states during shock-induced solid-liquid phase transitions in crystalline Al is followed using moving window molecular dynamics simulations. The orientation-dependent transition pathways towards an orientation-independent final state Hugoniot include both "cold melting" followed by recrystallization in [110]- and [111]-oriented shock waves and crystal overheating followed by melting in [100] shock waves. The orientation-dependent dynamics take place within a zone that can extend up to hundreds of nanometers behind the shock front.

Two-zone elastic-plastic single shock waves in solids.

By decoupling time and length scales in moving window molecular dynamics shock-wave simulations, a new regime of shock-wave propagation is uncovered characterized by a two-zone elastic-plastic shock-wave structure consisting of a leading elastic front followed by a plastic front, both moving with the same average speed and having a fixed net thickness that can extend to microns. The material in the elastic zone is in a metastable state that supports a pressure that can substantially exceed the critical pressure characteristic of the onset of the well-known split-elastic-plastic, two-wave propagation. The two-zone elastic-plastic wave is a general phenomenon observed in simulations of a broad class of crystalline materials and is within the reach of current experimental techniques.

Graphene growth on Ni(111) by transformation of a surface carbide.

A novel growth mechanism of graphene on Ni(111) has been discovered that occurs at temperatures below 460 °C. At these conditions, a surface-confined nickel-carbide phase coexists with single layer graphene. The graphene grows by in-plane transformation of the carbide along a one-dimensional phase-boundary, which is distinctively different from known growth processes on other transition metals and on Ni above 460 °C, where carbon atoms attach to "free" edges of graphene islands.